53 I

Halogen

Overview

Iodine is a chemical element; it has symbol I and atomic number 53. The heaviest of the stable halogens, it exists at standard conditions as a semi-lustrous, non-metallic solid 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, meaning 'violet'.
Iodine occurs in many oxidation states, including iodide (I−), iodate (IO−3), and the various periodate anions. As the heaviest essential mineral nutrient, iodine is required for 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. 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.

History

In 1811, iodine was discovered by French chemist Bernard Courtois, who was born to a family of manufacturers of saltpetre (an essential component of gunpowder). At the time of the Napoleonic Wars, saltpetre was in great demand in France. Saltpetre produced from French nitre beds required sodium carbonate, which could be isolated from seaweed collected on the coasts of Normandy and Brittany. To isolate the sodium carbonate, seaweed was burned and the ashes washed with water. While investigating the cause of corrosion to the copper vessels used in the process, Courtois added an excess of sulfuric acid to the waste remaining and a cloud of violet vapour arose. He noted that the vapour crystallised on cold surfaces, forming dark crystals. Courtois suspected that this material was a new element but lacked funding to pursue it further.
Courtois gave samples to his friends, Charles Bernard Desormes (1777–1838) and Nicolas Clément (1779–1841), to continue research. He also gave some of the substance to chemist Joseph Louis Gay-Lussac (1778–1850), and to physicist André-Marie Ampère (1775–1836). On 29 November 1813, Desormes and Clément made Courtois' discovery public by describing the substance to a meeting of the Imperial Institut de France. On 6 December 1813, Gay-Lussac found and announced that the new substance was either an element or a compound of oxygen and he found that it is an element. …

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. …

Sources & occurrence

Iodine is the least abundant of the stable halogens, comprising only 0.46 parts per million of Earth's crustal rocks (compare: fluorine: 544 ppm, chlorine: 126 ppm, bromine: 2.5 ppm) making it the 60th most abundant element. Iodide minerals are rare, and most deposits that are concentrated enough for economical extraction are iodate minerals instead. Examples include lautarite, Ca(IO3)2, and dietzeite, 7Ca(IO3)2·8CaCrO4. These are the minerals that occur as trace impurities in the caliche, found in Chile, whose main product is sodium nitrate. In total, they can contain at least 0.02% and at most 1% iodine by mass. Sodium iodate is extracted from the caliche and reduced to iodide by sodium bisulfite. This solution is then reacted with freshly extracted iodate, resulting in comproportionation to iodine, which may be filtered off.
The caliche was the main source of iodine in the 19th century and continues to be important today, replacing kelp (which is no longer an economically viable source), but in the late 20th century brines emerged as a comparable source. The Japanese Minami Kantō gas field east of Tokyo and the American Anadarko Basin gas field in northwest Oklahoma are the two largest such sources. The brine is hotter than 60 °C from the depth of the source. The brine is first purified and acidified using sulfuric acid, then the iodide present is oxidised to iodine with chlorine. An iodine solution is produced, but is dilute and must be concentrated. …

Uses

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.

As an element with high electron density and atomic number, iodine efficiently absorbs X-rays. X-ray radiocontrast agents is the top application for iodine. In this application, Organoiodine compounds are injected intravenously. 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-containing compounds.
Iodine absorbs X-rays with energies less than 33.3 keV due to the photoelectric effect of the innermost electrons.

Use of iodine as a biocide represents a major application of the element, ranked 2nd by weight. Elemental iodine (I2) is used as an antiseptic in medicine. A number of water-soluble compounds, from triiodide (I3−, generated in situ by adding iodide to poorly water-soluble elemental iodine) to various iodophors, slowly decompose to release I2 when applied.

Thin-film-transistor liquid crystal displays rely on polarisation. …

Isotopes

Naturally occurring iodine consists of one stable isotope, 127I, and is a mononuclidic element for atomic weight, which is thus a constant of nature determined by that isotope. Radioisotopes are known from 108I to 147I. As other isotopes have half-lives too short to be primordial, it is also monoisotopic.
The longest-lived of the radioactive isotopes of iodine is iodine-129, which has a half-life of 16.1 million years, decaying via beta decay to stable xenon-129. Some iodine-129 was formed along with iodine-127 before the formation of the Solar System, but it has by now completely decayed away, making it an extinct radionuclide. Its former presence may be determined from an excess of its daughter xenon-129, but early attempts to use this characteristic to date the supernova source for elements in the Solar System are made difficult by alternative nuclear processes giving iodine-129 and by iodine's volatility at higher temperatures. Due to its mobility in the environment iodine-129 has been used to date very old groundwaters.
The vast majority of iodine-129 on Earth today derives from human nuclear activity. Iodine-129 increased 3-8 orders of magnitude after nuclear activity began.
A small amount of naturally occurring iodine-129 forms from cosmic ray spallation of atmospheric xenon and as a fission product; the ratio 129I/127I is about 10−12.
Excited states of iodine-127 and iodine-129 are often used in Mössbauer spectroscopy. …

Hazards & biological role

Iodine is an essential element for life and, at atomic number Z = 53, is the heaviest element commonly needed by living organisms. (Lanthanum and the other lanthanides, as well as tungsten with Z = 74 and uranium with Z = 92, are used by a few microorganisms.) It is required for the synthesis of the growth-regulating thyroid hormones tetraiodothyronine and triiodothyronine (T4 and T3 respectively, named after their number of iodine atoms). A deficiency of iodine leads to decreased production of T3 and T4 and a concomitant enlargement of the thyroid tissue in an attempt to obtain more iodine, causing the disease goitre. The major form of thyroid hormone in the blood is tetraiodothyronine (T4), which has a longer life than triiodothyronine (T3). In humans, the ratio of T4 to T3 released into the blood is between 14:1 and 20:1. T4 is converted to the active T3 (three to four times more potent than T4) within cells by deiodinases (5'-iodinase). These are further processed by decarboxylation and deiodination to produce iodothyronamine (T1a) and thyronamine (T0a'). All three isoforms of the deiodinases are selenium-containing enzymes; thus metallic selenium is needed for triiodothyronine and tetraiodothyronine production.
Iodine accounts for 65% of the molecular weight of T4 and 59% of T3. …