Iodine: Difference between revisions

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{{Infobox iodine|engvar=en-GB}}
 
'''Iodine''' is a [[chemical element]]; it has [[Chemical symbol|symbol]] '''I''' and [[atomic number]] 53. The heaviest of the stable [[halogen]]s, it exists at [[Standard temperature and pressure|standard conditions]] as a semi-lustrous, non-metallic solid that melts to form a deep violet liquid at {{convert|114|C}}, and boils to a violet gas at {{convert|184|C}}. The element was discovered by the French chemist [[Bernard Courtois]] in 1811 and was named two years later in 1813 by [[Joseph Louis Gay-Lussac]], after the [[Ancient Greek]] {{lang|grc|Ιώδης}}, meaning 'violet'.
 
Iodine occurs in many oxidation states, including [[iodide]] (I<sup>−</sup>), [[iodate]] ({{chem|IO|3|-}}), and the various [[periodate]] anions. It is the least abundant of the stable [[halogen]]s, being the 60th most abundant element. As the heaviest essential [[Mineral (nutrient)|mineral nutrient]], iodine is required for the synthesis of [[thyroid hormones]].<ref name="lpi">{{cite web|url=http://lpi.oregonstate.edu/mic/minerals/iodine|title=Iodine|publisher=Micronutrient Information Center, [[Linus Pauling Institute]], [[Oregon State University]], Corvallis|date=2015|access-date=20 November 2017|archive-date=17 April 2015|archive-url=https://web.archive.org/web/20150417055246/http://lpi.oregonstate.edu/mic/minerals/iodine|url-status=live}}</ref> [[Iodine deficiency]] affects about two billion people and is the leading preventable cause of [[Intellectual disability|intellectual disabilities]].<ref>{{cite news|url= https://query.nytimes.com/gst/fullpage.html?res=9E05E3D81231F935A25751C1A9609C8B63|work=The New York Times|title=In Raising the World's I.Q., the Secret's in the Salt| vauthors = McNeil Jr DG |date=2006-12-16|access-date=2009-07-21|url-status=live|archive-url= https://web.archive.org/web/20100712011551/http://query.nytimes.com/gst/fullpage.html?res=9E05E3D81231F935A25751C1A9609C8B63|archive-date=2010-07-12}}</ref>
 
The dominant producers of iodine today are [[Chile]] and [[Japan]]. Due to its high atomic number and ease of attachment to [[organic compound]]s, it has also found favour as a non-toxic [[Radiocontrast agent|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 [[Catalysis|catalyst]] in the industrial production of [[acetic acid]] and some [[polymer]]s.
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==History==
In 1811, iodine was discovered by French [[chemist]] [[Bernard Courtois]],<ref name="court">{{cite journal| vauthors = Courtois B |title=Découverte d'une substance nouvelle dans le Vareck |trans-title=Discovery of a new substance in seaweed |journal=[[Annales de chimie]] |volume=88 |pages=304–310 |date=1813 |url=https://books.google.com/books?id=YGwri-w7sMAC&pg=RA2-PA304|language=French}} In French, seaweed that had been washed onto the shore was called "varec", "varech", or "vareck", whence the English word "wrack". Later, "varec" also referred to the ashes of such seaweed: the ashes were used as a source of iodine and salts of sodium and potassium.</ref><ref>{{cite journal | vauthors = Swain PA |title=Bernard Courtois (1777–1838) famed for discovering iodine (1811), and his life in Paris from 1798 |journal=Bulletin for the History of Chemistry |volume=30 |issue=2 |page=103 |date=2005 |url=http://www.scs.uiuc.edu/~mainzv/HIST/awards/OPA%20Papers/2007-Swain.pdf |access-date=2 April 2009 |archive-url=https://web.archive.org/web/20100714110757/http://www.scs.uiuc.edu/~mainzv/HIST/awards/OPA%20Papers/2007-Swain.pdf |archive-date=14 July 2010 |url-status=dead }}</ref> who was born to a family of manufacturers of [[potassium nitrate|saltpetre]] (an essential component of [[gunpowder]]). At the time of the [[Napoleonic Wars]], saltpetre was in great demand in [[France]]. Saltpetre produced from French [[Potassium nitrate|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 ash washed with water. The remaining waste was destroyed by adding [[Sulfuric acid|sulphuric acid]]. Courtois once added excessive sulphuric acid and a cloud of violet vapour rose. He noted that the vapour crystallised on cold surfaces, making dark black crystals.<ref name="Greenwood794">Greenwood and Earnshaw, p. 794</ref> Courtois found that this material was a new element and he did not have funding to pursue it further.<ref name="vdK">{{cite web |url=http://elements.vanderkrogt.net/element.php?sym=i |title=53 Iodine |publisher=Elements.vanderkrogt.net |access-date=23 October 2016 |archive-date=23 January 2010 |archive-url=https://web.archive.org/web/20100123001444/http://elements.vanderkrogt.net/element.php?sym=I |url-status=live }}</ref>
 
So Courtois gave the 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. They described the substance to a meeting of the Imperial [[Institut de France|Institute of France]].<ref>Desormes and Clément made their announcement at the Institut impérial de France on 29 November 1813; a summary of their announcement appeared in the ''Gazette nationale ou Le Moniteur Universel'' of 2 December 1813. See:
* {{cite journal |last1=(Staff) |title=Institut Imperial de France |journal=Le Moniteur Universel |date=2 December 1813 |issue=336 |page=1344 |url=https://www.retronews.fr/journal/gazette-nationale-ou-le-moniteur-universel/02-decembre-1813/149/1332251/2 |language=French |access-date=2 May 2021 |archive-date=28 November 2022 |archive-url=https://web.archive.org/web/20221128171041/https://www.retronews.fr/journal/gazette-nationale-ou-le-moniteur-universel/02-decembre-1813/149/1332251/2 |url-status=live }}
* {{cite journal |vauthors=Chattaway FD |title=The discovery of iodine |journal=Chemical News and Journal of Industrial Science |date=23 April 1909 |volume=99 |issue=2578 |pages=193–195 |url=https://books.google.com/books?id=Rco_AQAAIAAJ&pg=PA193 }}</ref> On 6 December 1813, Gay-Lussac found and announced that the new substance was either an element or a compound of [[oxygen]] with an another element and he found that it is an element without any oxygen in it.<ref name="Gay-Lussac">{{cite journal |vauthors=Gay-Lussac J |title=Sur un nouvel acide formé avec la substance décourverte par M. Courtois |trans-title=On a new acid formed by the substance discovered by Mr. Courtois |journal=Annales de Chimie |volume=88 |pages=311–318 |date=1813 |url=https://books.google.com/books?id=YGwri-w7sMAC&pg=PA311 |language=French |access-date=2 May 2021 |archive-date=19 March 2024 |archive-url=https://web.archive.org/web/20240319070023/https://books.google.com/books?id=YGwri-w7sMAC&pg=PA311#v=onepage&q&f=false |url-status=live }}</ref><ref>{{cite journal |vauthors=Gay-Lussac J |title=Sur la combination de l'iode avec d'oxigène |trans-title=On the combination of iodine with oxygen |journal=Annales de Chimie |volume=88 |pages=319–321 |date=1813 |url=https://books.google.com/books?id=YGwri-w7sMAC&pg=PA319 |language=French |access-date=2 May 2021 |archive-date=19 March 2024 |archive-url=https://web.archive.org/web/20240319070022/https://books.google.com/books?id=YGwri-w7sMAC&pg=PA319#v=onepage&q&f=false |url-status=live }}</ref><ref>{{cite journal| vauthors = Gay-Lussac J |title=Mémoire sur l'iode |trans-title=Memoir on iodine |journal=Annales de Chimie |volume=91 |pages=5–160|date=1814 |url=https://books.google.com/books?id=Efms0Fri1CQC&pg=PA5|language=French}}</ref> Gay-Lussac suggested the name "iode" (Englished as "iodine"), from the [[Ancient Greek]] {{lang|grc|Ιώδης}} ({{transliteration|grc|iodēs}}, "violet"), because of the colour of iodine vapour.<ref name="court" /><ref name="Gay-Lussac" /> Ampère had given some of his sample to British chemist [[Humphry Davy]] (1778–1829), who experimented on the substance and noted its similarity to [[chlorine]] and also found it as an element.<ref>{{cite journal |vauthors=Davy H |author-link=Humphry Davy |title=Sur la nouvelle substance découverte par M. Courtois, dans le sel de Vareck |trans-title=On the new substance discovered by Mr. Courtois in the salt of seaweed |journal=Annales de Chimie |volume=88 |pages=322–329 |date=1813 |url=https://books.google.com/books?id=YGwri-w7sMAC&pg=PA322 |language=French |access-date=2 May 2021 |archive-date=19 March 2024 |archive-url=https://web.archive.org/web/20240319070024/https://books.google.com/books?id=YGwri-w7sMAC&pg=PA322#v=onepage&q&f=false |url-status=live }}</ref> Davy sent a letter dated 10 December to the [[Royal Society|Royal Society of London]] stating that he had identified a new element called iodine.<ref>{{cite journal| vauthors = Davy H |author-link=Humphry Davy |title=Some experiments and observations on a new substance which becomes a violet coloured gas by heat |journal=Philosophical Transactions of the Royal Society of London |volume=104 |pages=74–93 |date=1 January 1814 |doi=10.1098/rstl.1814.0007 |doi-access=free }}</ref> Arguments erupted between Davy and Gay-Lussac over who identified iodine first, but both scientists found that both of them identified iodine first and also knew that Courtois is the first one to isolate the element.<ref name="vdK" />
 
In 1873, the French medical researcher [[Casimir Davaine]] (1812–1882) discovered the antiseptic action of iodine.<ref>{{cite journal |vauthors=Davaine C |title=Recherches relatives à l'action des substances dites ''antiseptiques'' sur le virus charbonneux |journal=Comptes rendus hebdomadaires des séances de l'Académie des Sciences |date=1873 |volume=77 |pages=821–825 |url=https://babel.hathitrust.org/cgi/pt?id=uiug.30112025711521&view=1up&seq=829 |trans-title=Investigations regarding the action of so-called ''antiseptic'' substances on the anthrax bacterium |language=French |access-date=2 May 2021 |archive-date=5 May 2021 |archive-url=https://web.archive.org/web/20210505013431/https://babel.hathitrust.org/cgi/pt?id=uiug.30112025711521&view=1up&seq=829 |url-status=live }}</ref> [[Antonio Grossich]] (1849–1926), an Istrian-born surgeon, was among the first to use [[Sterilization (microbiology)|sterilisation]] of the operative field. In 1908, he introduced tincture of iodine as a way to rapidly sterilise the human skin in the surgical field.<ref>{{cite journal |vauthors=Grossich A |title=Eine neue Sterilisierungsmethode der Haut bei Operationen |journal=Zentralblatt für Chirurgie |date=31 October 1908 |volume=35 |issue=44 |pages=1289–1292 |url=https://babel.hathitrust.org/cgi/pt?id=uc1.b4150494&view=1up&seq=1305 |trans-title=A new method of sterilization of the skin for operations |language=German |access-date=2 May 2021 |archive-date=5 May 2021 |archive-url=https://web.archive.org/web/20210505130854/https://babel.hathitrust.org/cgi/pt?id=uc1.b4150494 |url-status=live }}</ref>
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==Properties==
[[File:IodoAtomico.JPG|thumb|left|upright=0.7|alt=Round bottom flask filled with violet iodine vapour|Iodine vapour in a flask.]]
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 studied due to their expensiveness and inaccessibility in large quantities, but show various unusual properties for the group due to [[Relativistic quantum chemistry|relativistic effects]].) Iodine has an electron configuration of [Kr]4d<sup>10</sup>5s<sup>2</sup>5p<sup>5</sup>, with the seven electrons in the fifth and outermost shell being its [[valence electron]]s. 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 molecule]]s with chemical formula I<sub>2</sub>, 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<sup>−</sup>, is the strongest reducing agent among the stable halogens, being the most easily oxidised back to diatomic I<sub>2</sub>.<ref name="Greenwood800">Greenwood and Earnshaw, pp. 800–4</ref> (Astatine goes further, being indeed unstable as At<sup>−</sup> and readily oxidised to At<sup>0</sup> or At<sup>+</sup>.)<ref>{{cite book | series = Gmelin Handbook of Inorganic and Organometallic Chemistry | title = 'At, Astatine', System No. 8a | edition=8th | year = 1985 | publisher = Springer-Verlag | isbn = 978-3-540-93516-2 | vauthors = Kugler HK, Keller C | volume = 8 }}</ref>
 
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.
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Iodine is quite reactive, but it is much less reactive than the other halogens. For example, while [[chlorine]] gas will [[Halogenation|halogenate]] [[carbon monoxide]], [[nitric oxide]], and [[sulfur dioxide|sulphur dioxide]] (to [[phosgene]], [[nitrosyl chloride]], and [[sulfuryl chloride|sulphuryl 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(VI) chloride|rhenium hexachloride]], but with bromine it forms only rhenium pentabromide and iodine can achieve only rhenium tetraiodide.<ref name="Greenwood800" /> 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]].<ref name="Greenwood804" />
 
===Charge-transfer complexes ===
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===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 [[Halogenation|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|hydrogen sulphide]] or [[hydrazine]]:<ref name="Greenwood809">Greenwood and Earnshaw, pp. 809–12</ref>
:2 I<sub>2</sub> + N<sub>2</sub>H<sub>4</sub> {{overset|H<sub>2</sub>O|⟶}} 4 HI + N<sub>2</sub>
At room temperature, it is a colourless gas, like all of the hydrogen halides except [[hydrogen fluoride]], since hydrogen cannot form strong [[hydrogen bond]]s to the large and only mildly electronegative iodine atom. It melts at −51.0&nbsp;°C and boils at −35.1&nbsp;°C. It is an [[Endothermic process|endothermic]] compound that can exothermically dissociate at room temperature, although the process is very slow unless a [[Catalysis|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|bond dissociation energy]] is likewise the smallest of the hydrogen halides, at 295&nbsp;kJ/mol.<ref name="Greenwood812">Greenwood and Earnshaw, pp. 812–9</ref>
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===Iodine oxides and oxoacids===
[[File:Iodine-pentoxide-3D-balls.png|thumb|right|upright=0.7|Structure of iodine pentoxide]]
[[Iodine oxide]]s are the most stable of all the halogen oxides, because of the strong I–O bonds resulting from the large electronegativity difference between iodine and oxygen, and they have been known for the longest time.<ref name="King" /> The stable, white, [[Hygroscopy|hygroscopic]] [[iodine pentoxide]] (I<sub>2</sub>O<sub>5</sub>) has been known since its formation in 1813 by Gay-Lussac and Davy. It is most easily made by the dehydration of [[iodic acid]] (HIO<sub>3</sub>), of which it is the anhydride. It will quickly oxidise carbon monoxide completely to [[carbon dioxide]] at room temperature, and is thus a useful reagent in determining carbon monoxide concentration. It also oxidises [[nitrogen oxide]], [[ethylene]], and [[hydrogen sulfide|hydrogen sulphide]]. It reacts with [[sulfur trioxide|sulphur trioxide]] and peroxydisulphuryl difluoride (S<sub>2</sub>O<sub>6</sub>F<sub>2</sub>) to form salts of the iodyl cation, [IO<sub>2</sub>]<sup>+</sup>, and is reduced by concentrated [[sulfuric acid|sulphuric acid]] to iodosyl salts involving [IO]<sup>+</sup>. It may be fluorinated by [[fluorine]], [[bromine trifluoride]], [[sulfur tetrafluoride|sulphur tetrafluoride]], or [[chloryl fluoride]], resulting [[iodine pentafluoride]], which also reacts with [[iodine pentoxide]], giving iodine(V) oxyfluoride, IOF<sub>3</sub>. A few other less stable oxides are known, notably I<sub>4</sub>O<sub>9</sub> and I<sub>2</sub>O<sub>4</sub>; their structures have not been determined, but reasonable guesses are I<sup>III</sup>(I<sup>V</sup>O<sub>3</sub>)<sub>3</sub> and [IO]<sup>+</sup>[IO<sub>3</sub>]<sup>−</sup> respectively.<ref name="Greenwood851">Greenwood and Earnshaw, pp. 851–3</ref>
 
{| class="wikitable" style="float:right; margin-top:0; margin-left:1em; text-align:center; font-size:10pt; line-height:11pt; width:25%;"
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:{{chem|IO|3|-}} + 6 OH<sup>−</sup> + Cl<sub>2</sub> → {{chem|IO|6|5-}} + 2 Cl<sup>−</sup> + 3 H<sub>2</sub>O
 
They are thermodymically and kinetically powerful oxidising agents, quickly oxidising Mn<sup>2+</sup> to [[permanganate|{{chem|MnO|4|-}}]], and cleaving [[Diol|glycols]], α-[[Dicarbonyl|diketones]], α-[[Hydroxy ketone|ketols]], α-[[Alkanolamine|aminoalcohols]], and α-[[diamine]]s.<ref name="Greenwood872" /> Orthoperiodate especially stabilises high oxidation states among metals because of its very high negative charge of −5. [[Periodic acid|Orthoperiodic acid]], H<sub>5</sub>IO<sub>6</sub>, is stable, and dehydrates at 100&nbsp;°C in a vacuum to [[Periodic acid|Metaperiodic acid]], HIO<sub>4</sub>. Attempting to go further does not result in the nonexistent iodine heptoxide (I<sub>2</sub>O<sub>7</sub>), but rather iodine pentoxide and oxygen. Periodic acid may be protonated by [[sulfuric acid|sulphuric acid]] to give the {{chem|I(OH)|6|+}} cation, isoelectronic to Te(OH)<sub>6</sub> and {{chem|Sb(OH)|6|-}}, and giving salts with bisulfate and sulfate.<ref name="King" />
 
===Polyiodine compounds===
When iodine dissolves in strong acids, such as fuming sulphuric acid, a bright blue [[Paramagnetism|paramagnetic]] solution including {{chem|I|2|+}} cations is formed. A solid salt of the diiodine cation may be obtained by oxidising iodine with [[antimony pentafluoride]]:<ref name="King" />
:2 I<sub>2</sub> + 5 SbF<sub>5</sub> {{overunderset|{{big|⟶}}|SO<sub>2</sub>|20&nbsp;°C}} 2 I<sub>2</sub>Sb<sub>2</sub>F<sub>11</sub> + SbF<sub>3</sub>
The salt I<sub>2</sub>Sb<sub>2</sub>F<sub>11</sub> is dark blue, and the blue [[tantalum]] analogue I<sub>2</sub>Ta<sub>2</sub>F<sub>11</sub> is also known. Whereas the I–I bond length in I<sub>2</sub> is 267&nbsp;pm, that in {{chem|I|2|+}} is only 256&nbsp;pm as the missing electron in the latter has been removed from an antibonding orbital, making the bond stronger and hence shorter. In [[fluorosulfuric acid|fluorosulphuric acid]] solution, deep-blue {{chem|I|2|+}} reversibly dimerises below −60&nbsp;°C, forming red rectangular diamagnetic {{chem|I|4|2+}}. Other polyiodine cations are not as well-characterised, including bent dark-brown or black {{chem|I|3|+}} and centrosymmetric ''C''<sub>2''h''</sub> green or black {{chem|I|5|+}}, known in the {{chem|AsF|6|-}} and {{chem|AlCl|4|-}} salts among others.<ref name="King" /><ref name="Greenwood842">Greenwood and Earnshaw, pp. 842–4</ref>
 
The only important polyiodide anion in aqueous solution is linear [[triiodide]], {{chem|I|3|-}}. Its formation explains why the solubility of iodine in water may be increased by the addition of potassium iodide solution:<ref name="King" />
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:[[Image:Iodoform synthesis.svg|450px]]
 
Some drawbacks of using organoiodine compounds as compared to organochlorine or organobromine compounds is the greater expense and toxicity of the iodine derivatives, since iodine is expensive and organoiodine compounds are stronger alkylating agents.<ref>{{cite web|publisher = Oxford University|title = Safety data for iodomethane|url = http://msds.chem.ox.ac.uk/IO/iodomethane.html|access-date = 12 December 2008|archive-date = 10 August 2010|archive-url = https://web.archive.org/web/20100810211004/http://msds.chem.ox.ac.uk/IO/iodomethane.html|url-status = dead}}</ref> For example, [[iodoacetamide]] and [[iodoacetic acid]] denature proteins by irreversibly alkylating [[cysteine]] residues and preventing the reformation of [[disulfide|disulphide]] linkages.<ref>{{cite journal | vauthors = Polgár L | title = Deuterium isotope effects on papain acylation. Evidence for lack of general base catalysis and for enzyme--leaving-group interaction | journal = European Journal of Biochemistry | volume = 98 | issue = 2 | pages = 369–374 | date = August 1979 | pmid = 488108 | doi = 10.1111/j.1432-1033.1979.tb13196.x | doi-access = free }}</ref>
 
Halogen exchange to produce iodoalkanes by the [[Finkelstein reaction]] is slightly complicated by the fact that iodide is a better leaving group than chloride or bromide. The difference is nevertheless small enough that the reaction can be driven to completion by exploiting the differential solubility of halide salts, or by using a large excess of the halide salt.<ref name="March" /> In the classic Finkelstein reaction, an [[Organochlorine chemistry|alkyl chloride]] or an [[Organobromine chemistry|alkyl bromide]] is converted to an [[Organoiodine chemistry|alkyl iodide]] by treatment with a solution of [[sodium iodide]] in [[acetone]]. Sodium iodide is soluble in acetone and [[sodium chloride]] and [[sodium bromide]] are not.<ref>{{cite journal | vauthors = Ervithayasuporn V, Ervithayasuporn V, Pornsamutsin N, Pornsamutsin N, Prangyoo P, Prangyoo P, Sammawutthichai K, Sammawutthichai K, Jaroentomeechai T, Jaroentomeechai T, Phurat C, Phurat C, Teerawatananond T, Teerawatananond T | title = One-pot synthesis of halogen exchanged silsesquioxanes: octakis(3-bromopropyl)octasilsesquioxane and octakis(3-iodopropyl)octasilsesquioxane | journal = Dalton Transactions | volume = 42 | issue = 37 | pages = 13747–13753 | date = October 2013 | pmid = 23907310 | doi = 10.1039/C3DT51373D | s2cid = 41232118 }}</ref> The reaction is driven toward products by [[Law of mass action|mass action]] due to the precipitation of the insoluble salt.<ref>{{cite journal | vauthors = Streitwieser A | year = 1956 | title = Solvolytic Displacement Reactions at Saturated Carbon Atoms | journal = [[Chem. Rev.]] | volume = 56 | pages = 571–752 | doi = 10.1021/cr50010a001 | issue = 4}}</ref><ref>{{cite journal | title = The Effect of the Carbonyl and Related Groups on the Reactivity of Halides in S<sub>N</sub>2 Reactions | vauthors = Bordwell FG, Brannen WT | journal = [[J. Am. Chem. Soc.]] | year = 1964 | volume = 86 | pages = 4645–4650 | doi = 10.1021/ja01075a025 | issue = 21}}</ref>
 
==Occurrence and production==
Iodine is the least abundant of the stable halogens, comprising only 0.46&nbsp;[[Parts-per notation|parts per million]] of Earth's crustal rocks (compare: [[fluorine]]: 544&nbsp;ppm, [[chlorine]]: 126&nbsp;ppm, [[bromine]]: 2.5&nbsp;ppm) making it the 60th most abundant element.<ref name="Greenwood795">Greenwood and Earnshaw, pp. 795–796.</ref> Iodide minerals are rare, and most deposits that are concentrated enough for economical extraction are iodate minerals instead. Examples include [[Calcium iodate|lautarite]], Ca(IO<sub>3</sub>)<sub>2</sub>, and dietzeite, 7Ca(IO<sub>3</sub>)<sub>2</sub>·8CaCrO<sub>4</sub>.<ref name="Greenwood795" /> 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.<ref name="Elzea">{{cite book |title = Industrial Minerals & Rocks: Commodities, Markets, and Uses |publisher = SME |date = 2006 |isbn = 978-0-87335-233-8 |url = https://books.google.com/books?id=zNicdkuulE4C |pages = 541–552 | veditors = Kogel JE, Trivedi NC, Barker JM, Krukowski ST }}</ref> [[Sodium iodate]] is extracted from the caliche and reduced to iodide by [[sodium bisulfite|sodium bisulphite]]. This solution is then reacted with freshly extracted iodate, resulting in comproportionation to iodine, which may be filtered off.<ref name="Greenwood800" />
 
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),<ref>{{cite journal |url = https://books.google.com/books?id=wW8KAAAAIAAJ&pg=PA185 | vauthors = Stanford EC |journal = Journal of the Society of Arts |title = On the Economic Applications of Seaweed |date = 1862 |pages = 185–189}}</ref> but in the late 20th century [[brine]]s 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&nbsp;°C from the depth of the source. The [[brine]] is first [[List of purification methods in chemistry|purified]] and acidified using [[sulfuric acid|sulphuric acid]], then the iodide present is oxidised to iodine with [[chlorine]]. An iodine solution is produced, but is dilute and must be concentrated. Air is blown into the solution to [[Evaporation|evaporate]] the iodine, which is passed into an absorbing tower, where [[sulfur dioxide|sulphur dioxide]] reduces the iodine. The [[hydrogen iodide]] (HI) is reacted with chlorine to precipitate the iodine. After filtering and purification the iodine is packed.<ref name="Elzea" /><ref>{{cite journal |journal = Geochemical Journal |volume = 40 |page = 475 |date = 2006 |title = Chemical and isotopic compositions of brines from dissolved-in-water type natural gas fields in Chiba, Japan | vauthors = Maekawa T, Igari SI, Kaneko N |doi = 10.2343/geochemj.40.475 |issue = 5 |bibcode = 2006GeocJ..40..475M|doi-access = free }}</ref>
 
: 2 HI + Cl<sub>2</sub> → I<sub>2</sub>↑ + 2 HCl
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: 2 HI + Cl<sub>2</sub> → I<sub>2</sub>↓ + 2 HCl
 
These sources ensure that Chile and Japan are the largest producers of iodine today.<ref name="Greenwood795" /> Also, the brine is treated with [[silver nitrate]] to precipitate out iodine as [[silver iodide]], which is then decomposed by reaction with iron to form metallic silver and a solution of [[iron(II) iodide]]. The iodine is then liberated by displacement with [[chlorine]].<ref name="Greenwood799">Greenwood and Earnshaw, p. 799.</ref>
 
==Applications==
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===Spacecraft propulsion===
[[Ion thruster]] propulsion systems employing iodine as the [[working mass|reaction mass]] can be built more compactly, with less mass (and cost), and operate more efficiently than the [[gridded ion thruster]]s that were utilized to propel previous spacecraft, such as Japan's [[Hayabusa]] probes, ESA's [[Gravity Field and Steady-State Ocean Circulation Explorer|GOCE]] satellite, or NASA's [[Double Asteroid Redirection Test|DART]] mission, all of which used xenon for this purpose. Iodine's [[Standard atomic weight|atomic weight]] is only 3.3% less than that of xenon, while its first two [[Ionization energy|ionisation energies]] average 12% less; together, these make iodine ions a promising substitute.<ref name="ThrustMe1">{{cite journal |vauthors=Rafalskyi D, Martínez JM, Habl L, Zorzoli Rossi E, Proynov P, Boré A, Baret T, Poyet A, Lafleur T, Dudin S, Aanesland A |date=November 2021 |title=In-orbit demonstration of an iodine electric propulsion system |journal=Nature |volume=599 |issue=7885 |pages=411–415 |bibcode=2021Natur.599..411R |doi=10.1038/s41586-021-04015-y |pmc=8599014 |pmid=34789903 |quote=''Both atomic and molecular iodine ions are accelerated by high-voltage grids to generate thrust, and a highly collimated beam can be produced with substantial iodine dissociation.''}}</ref><ref name="ThrustMe2">{{cite web |url=https://www.cnet.com/news/in-a-space-first-scientists-test-ion-thrusters-powered-by-iodine/ |title=In a space first, scientists test ion thrusters powered by iodine |vauthors=Ravisetti M |date=18 November 2021 |website=[[CNET]] |publisher=[[Red Ventures]] |access-date=2021-11-29 |archive-date=27 November 2021 |archive-url=https://web.archive.org/web/20211127105437/https://www.cnet.com/news/in-a-space-first-scientists-test-ion-thrusters-powered-by-iodine/ |url-status=live }}</ref> However, iodine introduces chemical reactivity issues not present in xenon plasmas.<ref>Rogers, James Daniel. ''Hollow Cathode Materials in an Iodine Plasma Enviroment''. Diss. The University of Alabama, 2023.</ref>
 
Use of iodine should allow more widespread application of ion-thrust technology, particularly with smaller-scale space vehicles.<ref name="ThrustMe2" /> According to the [[European Space Agency]], "This small but potentially disruptive innovation could help to clear the skies of [[space debris|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."<ref name="ThrustMe3">{{cite web |url=https://www.esa.int/ESA_Multimedia/Images/2021/01/Iodine_thruster_used_to_change_the_orbit_of_a_small_satellite_for_the_first_time_ever#.YaUuCq-kYyQ.link |title=Iodine thruster used to change the orbit of a small satellite for the first time ever |author=<!--Not stated--> |date=22 January 2021 |website=www.esa.int |publisher=The European Space Agency |access-date=2021-11-29 |archive-date=29 November 2021 |archive-url=https://web.archive.org/web/20211129202716/https://www.esa.int/ESA_Multimedia/Images/2021/01/Iodine_thruster_used_to_change_the_orbit_of_a_small_satellite_for_the_first_time_ever#.YaUuCq-kYyQ.link |url-status=live }}</ref>
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Salts of iodide and iodate are used at low doses in [[iodised salt]]. A saturated solution of [[potassium iodide]] is used to treat acute [[Hyperthyroidism|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.<ref>{{cite web |url=http://hazard.com/msds/mf/baker/baker/files/p5906.htm |title=Solubility of KI in water |publisher=Hazard.com |date=1998-04-21 |access-date=2013-01-21 |archive-date=23 April 2012 |archive-url=https://web.archive.org/web/20120423195709/http://hazard.com/msds/mf/baker/baker/files/p5906.htm |url-status=live }}</ref><ref>{{cite web|url=http://www.eanm.org/scientific_info/guidelines/gl_radio_ther_benzyl.pdf|archive-url=https://web.archive.org/web/20090617073253/http://www.eanm.org/scientific_info/guidelines/gl_radio_ther_benzyl.pdf | title=EANM procedure guidelines for 131I-meta-iodobenzylguanidine (131I-mIBG) therapy|url-status=dead|archive-date=17 June 2009|date=17 June 2009}}</ref>
 
[[File:Diatrizoic acid.svg|thumb|right|[[Diatrizoate|Diatrizoic acid]], an iodine-containing radiocontrast agent]]
 
As an element with high [[electron density]] and atomic number, iodine absorbs X-rays weaker than 33.3&nbsp;keV due to the [[photoelectric effect]] of the innermost electrons.<ref>{{cite book | vauthors = Lancaster JL | chapter-url = http://ric.uthscsa.edu/personalpages/lancaster/DI-II_Chapters/DI_chap4.pdf | chapter = Chapter 4: Physical Determinants of Contrast | archive-url =https://web.archive.org/web/20151010172937/http://ric.uthscsa.edu/personalpages/lancaster/DI-II_Chapters/DI_chap4.pdf | archive-date=10 October 2015 | title = Physics of Medical X-Ray Imaging | publisher = The University of Texas Health Science Center }}</ref> Organoiodine compounds are used with intravenous injection as X-ray [[Radiocontrast agent|radiocontrast]] agents. This application is often in conjunction with advanced X-ray techniques such as [[angiography]] and [[CT scan]]ning. At present, all water-soluble radiocontrast agents rely on [[Iodinated contrast|iodine-containing compounds]].
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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.<ref name = Ullmann/>
 
The organoiodine compound [[erythrosine]] is an important food coloring agent. Perfluoroalkyl iodides are precursors to important surfactants, such as [[perfluorooctanesulfonic acid|perfluorooctanesulphonic acid]].<ref name = Ullmann/>
 
The [[iodine clock reaction]] (in which iodine also serves as a test for starch, forming a dark blue complex),<ref name="Greenwood800" /> is a popular educational demonstration experiment and example of a seemingly oscillating reaction (it is only the concentration of an intermediate product that oscillates).
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===Dietary recommendations and intake===
The daily levels of intake recommended by the [[United States]] [[National Academy of Medicine]] are between 110 and 130 [[microgram|µg]] for infants up to 12 months, 90&nbsp;µg for children up to eight years, 130&nbsp;µg for children up to 13 years, 150&nbsp;µg for adults, 220&nbsp;µg for pregnant women and 290&nbsp;µg for lactating women.<ref name="lpi" /><ref>{{cite web|url=http://iom.edu/en/Global/News%20Announcements/~/media/Files/Activity%20Files/Nutrition/DRIs/DRISummaryListing2.ashx |archive-url=https://web.archive.org/web/20091030004039/http://iom.edu/en/Global/News%20Announcements/~/media/Files/Activity%20Files/Nutrition/DRIs/DRISummaryListing2.ashx |url-status=dead |archive-date=30 October 2009 |title=Dietary Reference Intakes (DRIs): Recommended Intakes for Individuals, Vitamins |publisher=[[Institute of Medicine]] |date=2004 |access-date=9 June 2010 }}</ref> The Tolerable Upper Intake Level (TUIL) for adults is 1,100&nbsp;μg/day.<ref name="InstituteofMedicine">{{cite book| author = United States National Research Council| date = 2000| title = Dietary Reference Intakes for Vitamin A, Vitamin K, Arsenic, Boron, Chromium, Copper, Iodine, Iron, Manganese, Molybdenum, Nickel, Silicon, Vanadium, and Zinc| pages = 258–259| publisher = National Academies Press| url = http://books.nap.edu/openbook.php?record_id=10026&page=258| doi = 10.17226/10026| pmid = 25057538| isbn = 978-0-309-07279-3| access-date = 9 March 2008| archive-date = 25 July 2015| archive-url = https://web.archive.org/web/20150725203752/http://books.nap.edu/openbook.php?record_id=10026&page=258| url-status = live}}</ref> This upper limit was assessed by analyzing the effect of supplementation on [[thyroid-stimulating hormone]].<ref name="Patrick2008" />
 
The [[European Food Safety Authority]] (EFSA) refers to the collective set of information as Dietary Reference Values, with Population Reference Intake (PRI) instead of RDA, and Average Requirement instead of EAR; AI and UL are defined the same as in the United States. For women and men ages 18 and older, the PRI for iodine is set at 150&nbsp;μg/day; the PRI during pregnancy and lactation is 200&nbsp;μg/day. For children aged 1–17 years, the PRI increases with age from 90 to 130&nbsp;μg/day. These PRIs are comparable to the U.S. RDAs with the exception of that for lactation.<ref>{{cite web| title = Overview on Dietary Reference Values for the EU population as derived by the EFSA Panel on Dietetic Products, Nutrition and Allergies| year = 2017| url = https://www.efsa.europa.eu/sites/default/files/assets/DRV_Summary_tables_jan_17.pdf| access-date = 3 December 2023| archive-date = 28 August 2017| archive-url = https://web.archive.org/web/20170828082247/https://www.efsa.europa.eu/sites/default/files/assets/DRV_Summary_tables_jan_17.pdf| url-status = live}}</ref>
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Natural food sources of iodine include [[seafood]] which contains [[fish]], [[Seaweed|seaweeds]], [[kelp]], [[shellfish]] and other [[Food|foods]] which contain [[Dairy product|dairy products]], [[Eggs as food|eggs]], [[Meat|meats]], [[Vegetable|vegetables]], so long as the animals ate iodine richly, and the plants are grown on iodine-rich soil.<ref>{{cite web| publisher =Iodine Global Network|url =http://ign.org/p142002146.html|archive-url=https://web.archive.org/web/20150813130042/http://ign.org/p142002146.html|archive-date=13 August 2015|title=Where do we get iodine from?|url-status=live}}</ref><ref name = medlineplus002421/> [[Iodised salt]] is fortified with [[potassium iodate]], a salt of iodine, potassium, oxygen.<ref name="medlineplus002421">{{cite encyclopedia| url = https://www.nlm.nih.gov/medlineplus/ency/article/002421.htm| title = Iodine in diet| encyclopedia = MedlinePlus Medical Encyclopedia| access-date = 7 April 2016| archive-date = 5 July 2016| archive-url = https://web.archive.org/web/20160705122918/https://www.nlm.nih.gov/medlineplus/ency/article/002421.htm| url-status = live}}</ref><ref name="American Thyroid Association">{{cite web|title=American Thyroid Association|url=http://www.thyroid.org/iodine-deficiency/|work=thyroid.org|publisher=American Thyroid Association|access-date=4 April 2014|archive-date=3 August 2023|archive-url=https://web.archive.org/web/20230803045045/https://www.thyroid.org/iodine-deficiency/|url-status=dead}}</ref><ref>{{cite web | url = https://www.waitrose.com/ecom/products/cerebos-iodised-table-salt/559124-79136-79137 | title = Cerebos iodised table salt | year = 2023 | website = [[Waitrose]] | access-date = 2023-05-30 | archive-url = https://web.archive.org/web/20230328192627/https://www.waitrose.com/ecom/products/cerebos-iodised-table-salt/559124-79136-79137 | archive-date = 2023-03-28}}</ref>
 
As of 2000, the median intake of iodine from food in the United States was 240 to 300&nbsp;μg/day for men and 190 to 210&nbsp;μg/day for women.<ref name="InstituteofMedicine" /> The general US population has adequate iodine nutrition,<ref>{{cite journal | vauthors = Caldwell KL, Makhmudov A, Ely E, Jones RL, Wang RY | title = Iodine status of the U.S. population, National Health and Nutrition Examination Survey, 2005–2006 and 2007–2008 | journal = Thyroid | volume = 21 | issue = 4 | pages = 419–427 | date = April 2011 | pmid = 21323596 | doi = 10.1089/thy.2010.0077 | url = https://zenodo.org/record/1235283 | access-date = 29 September 2020 | archive-date = 2 December 2022 | archive-url = https://web.archive.org/web/20221202135223/https://zenodo.org/record/1235283 | url-status = live }}</ref><ref name="Lueng">{{cite journal | vauthors = Leung AM, Braverman LE, Pearce EN | title = History of U.S. iodine fortification and supplementation | journal = Nutrients | volume = 4 | issue = 11 | pages = 1740–1746 | date = November 2012 | pmid = 23201844 | pmc = 3509517 | doi = 10.3390/nu4111740 | doi-access = free }}</ref> with lactating women and pregnant women having a mild risk of deficiency.<ref name="Lueng" /> In Japan, consumption was considered much higher, ranging between 5,280&nbsp;μg/day to 13,800&nbsp;μg/day from [[wakame]] and [[kombu]] that are eaten,<ref name="Patrick2008">{{cite journal | vauthors = Patrick L | title = Iodine: deficiency and therapeutic considerations | journal = Alternative Medicine Review | volume = 13 | issue = 2 | pages = 116–127 | date = June 2008 | pmid = 18590348 | url = http://www.thorne.com/altmedrev/.fulltext/13/2/116.pdf | url-status = dead | archive-url = https://web.archive.org/web/20130531112100/http://www.thorne.com/altmedrev/.fulltext/13/2/116.pdf | archive-date = 31 May 2013 }}</ref> both in the form of kombu and wakame and kombu and wakame [[umami]] [[Extract|extracts]] for [[Stock (food)|soup stock]] and [[Potato chip|potato chips]]. However, new studies suggest that Japan's consumption is closer to 1,000–3,000&nbsp;μg/day.<ref>{{cite journal | vauthors = Zava TT, Zava DT | title = Assessment of Japanese iodine intake based on seaweed consumption in Japan: A literature-based analysis | journal = Thyroid Research | volume = 4 | pages = 14 | date = October 2011 | pmid = 21975053 | pmc = 3204293 | doi = 10.1186/1756-6614-4-14 | doi-access = free }}</ref> The adult UL in Japan was last revised to 3,000&nbsp;µg/day in 2015.<ref>{{cite web |title=Overview of Dietary Reference Intakes for Japanese (2015) |publisher=Minister of Health, Labour and Welfare, Japan |url=http://www.mhlw.go.jp/file/06-Seisakujouhou-10900000-Kenkoukyoku/Overview.pdf |access-date=14 March 2022 |archive-date=23 April 2021 |archive-url=https://web.archive.org/web/20210423083531/https://www.mhlw.go.jp/file/06-Seisakujouhou-10900000-Kenkoukyoku/Overview.pdf |url-status=live }}</ref>
 
After iodine fortification programs such as iodisation of [[Sodium chloride|salt]] have been done, some cases of iodine-induced [[hyperthyroidism]] have been observed (so-called [[Jod-Basedow phenomenon]]). The condition occurs mainly in people above 40 years of age, and the risk is higher when iodine deficiency is high and the first rise in iodine consumption is high.<ref>{{cite journal | vauthors = Wu T, Liu GJ, Li P, Clar C | title = Iodised salt for preventing iodine deficiency disorders | journal = The Cochrane Database of Systematic Reviews | volume = 2010 | issue = 3 | pages = CD003204 | date = 2002 | pmid = 12137681 | pmc = 9006116 | doi = 10.1002/14651858.CD003204 | veditors = Wu T }}</ref>