Iodine

Iodine (IPA: /ˈaɪədaɪn, ˈaɪədɪn/, or /ˈaɪədiːn/; from Greek: iodes "violet"), is a chemical element that has the symbol I and atomic number 53. Iodine has 53 protons, 53 electrons, and 74 neutrons. Chemically, iodine is the least reactive of the halogens, and the most electropositive halogen after astatine. Iodine is primarily used in medicine, photography and dyes. It is required in trace amounts by most living organisms.

As with all other halogens (members of Group VII in the Periodic Table), iodine forms diatomic molecules, and hence has the molecular formula of I₂.

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Characteristics

Iodine is a dark-gray/purple-brown solid that sublimes at standard temperatures into a purple-pink gas that has an irritating odor. This halogen forms compounds with many elements, but is less active than the other members of its Group VII (halogens) and has some metallic-like properties. Iodine dissolves easily in chloroform, carbon tetrachloride. The solubility of elementary iodine in water can be vastly increased by the addition of potassium iodide. The molecular iodine reacts reversibly with the negative ion, creating the triiodide anion, I₃⁻, which dissolves well in water. This is also the formulation of medicinal iodine of old. The deep blue color of starch-iodine complexes is produced only by the free element.

Many students who have seen the classroom demonstration where iodine crystals are gently heated in a test tube come away with the impression that liquid iodine cannot exist at atmospheric pressure. This misconception arises because sublimation occurs without the intermediacy of liquid. The truth is that if iodine crystals are heated carefully to their melting point of 113.7 °C, the crystals will fuse into a liquid, which will be present under a dense blanket of the vapour.

History

Iodine was discovered by Bernard Courtois in 1811. He was born to a manufacturer of saltpeter (a vital part of gunpowder). At the time of the Napoleonic Wars, France was at war and saltpeter was in great demand. Saltpeter produced from French niter beds required sodium carbonate, which could be isolated from seaweed washed up on the coasts of Normandy and Brittany. To isolate the sodium carbonate, seaweed was burned and the ash then washed with water. The remaining waste was destroyed by adding sulfuric acid. One day Courtois added too much sulfuric acid and a cloud of purple vapor rose. Courtois noted that the vapor crystallized on cold surfaces making dark crystals. Courtois suspected that this was a new element but lacked the money to pursue his observations.

However he gave samples to his friends, Charles Bernard Desormes (1777 - 1862) and Nicolas Clément (1779 - 1841), to continue research. He also gave some of the substance to Joseph Louis Gay-Lussac (1778 - 1850), a well-known chemist at that time, and to André-Marie Ampère (1775 - 1836). On 29 November 1813, Dersormes and Clément made public Courtois’ discovery. They described the substance to a meeting of the Imperial Institute of France. On December 6, Gay-Lussac announced that the new substance was either an element or a compound of oxygen. Ampère had given some of his sample to Humphry Davy (1778 - 1829). Davy did some experiments on the substance and noted its similarity to chlorine. Davy sent a letter dated December 10 to the Royal Society of London stating that he had identified a new element. A large argument erupted between Davy and Gay-Lussac over who identified iodine first but both scientists acknowledged Courtois as the first to isolate the chemical element.

Applications

Iodine is used in pharmaceuticals, antiseptics, medicine, food supplements, dyes, catalysts, halogen lights, photography, water purifying, and starch detection.

• Tincture of iodine (10% elemental iodine in ethanol base) is an essential component of any emergency survival kit, used both to disinfect wounds and to sanitize surface water for drinking (3 drops per litre, let stand for 30 minutes). Alcohol-free iodine solutions such as Lugol's iodine, as well as other iodophor type antiseptics, are also available as effective elemental iodine sources for this purpose.
• Iodine compounds are important in the field of organic chemistry
• Iodine, as a heavy element, is quite radio-opaque. Organic compounds of a certain type (typically iodine-substituted benzene derivatives) are thus used in medicine as X-ray radiocontrast agents for intravenous injection. This is often in conjunction with advanced X-ray techniques such as angiography and CT scanning
• Silver iodide is used in photography.
• Tungsten iodide is used to stabilize the filaments in light bulbs.

Occurrence on earth

Iodine naturally occurs in the environment chiefly as dissolved iodide in seawater, although it is also found in some minerals and soils. The element may be prepared in an ultrapure form through the reaction of potassium iodide with copper(II) sulfate. There are also a few other methods of isolating this element. Although the element is actually quite rare, kelp and certain other plants have some ability to concentrate iodine, which helps introduce the element into the food chain as well as keeping its cost down.

Sources

  Iodine is found in the mineral caliche, found in Chile, between the Andes and the sea. It can also be found in some seaweeds as well as extracted from seawater, however extracting iodine from the mineral is the only economical way to extract the substance.^{[citation needed]}

Extraction from seawater involves electrolysis. The brine is first purified and acidified using sulphuric acid and is then reacted with chlorine. An iodine solution is produced but it is yet too dilute and has to be concentrated. To do this air is blown into the solution which causes the iodine to evaporate, then it is passed into an absorbing tower containing acid where sulfur dioxide is added to reduce the iodine. The solution is then added to chlorine again to concentrate the solution more, and the final solution is at a level of about 99%.^{[citation needed]}

Another source is from kelp. This source was used in the 18th and 19th centuries but is no longer economically viable.

In 2005, Chile was the top producer of iodine with almost two-thirds world share followed by Japan and the USA, reports the British Geological Survey.

Prices

The average price for iodine in 2005 was $7.03 US dollars per kilogram. In 2006 this suddenly changed to $17.03 US dollars per kilogram. In Chile, the world’s largest producer of iodine, prices dramatically changed too (2005 $16.97 US dollars 2006 $20.00 US dollars for one kilogram). Japan’s prices of iodine also changed. The DNSC (Defence National Stockpile Center) claims they sold one kilogram of iodine in 2005 for $18.36 US dollars. Then in 2006 they claimed they sold each kilogram for $21.29 US dollars. ^[1]

Descriptive chemistry

Elemental iodine is poorly soluble in water, with one gram dissolving in 3450 ml at 20 °C and 1280 ml at 50 °C. By contrast with chlorine, the formation of the hypohalite ion (IO^–) in neutral aqueous solutions of iodine is negligible.

I₂+ H₂O ↔ H⁺ + I^– + HIO   (K = 2.0×10^-13) ^[2]

Solubility in water is greatly improved if the solution contains dissolved iodides such as hydroiodic acid, potassium iodide, or sodium iodide. Dissolved bromides also improve water solubility of iodine. Iodine is soluble in a number of organic solvents, including ethanol (20.5 g/100 ml at 15 °C, 21.43 g/100 ml at 25 °C), diethyl ether (20.6 g/100 ml at 17 °C, 25.20 g/100 ml at 25 °C), chloroform, acetic acid, glycerol, benzene (14.09 g/100 ml at 25 °C), carbon tetrachloride (2.603 g/100 ml at 35 °C), and carbon disulfide (16.47 g/100 ml at 25 °C)^[3]. Aqueous and ethanol solutions are brown. Solutions in chloroform, carbon tetrachloride, and carbon disulfide are violet.

Elemental iodine can be prepared by oxidizing iodides with chlorine:

2I^– + Cl₂ → I₂ + 2Cl^–

or with manganese dioxide in acid solution:^[2]

2I^– + 4H⁺ + MnO₂ → I₂ + 2H₂O + Mn²⁺

Iodine is reduced to hydroiodic acid by hydrogen sulfide:^[4]

I₂ + H₂S → 2HI + S↓

or by hydrazine:

2I₂ + N₂H₄ → 4HI + N₂

Iodine is oxidized to iodate by nitric acid:^[5]

I₂ + 10HNO₃ → 2HIO₃ + 10NO₂ + 4H₂O

or by chlorates:^[5]

I₂ + 2ClO₃^– → 2IO₃^– + Cl₂

Iodine is converted in a two stage reaction to iodide and iodate in solutions of alkali hydroxides (such as sodium hydroxide):^[2]

I2 + 2OH– → I– + IO– + H2O		(K = 30)
3IO– → 2I– + IO3–		(K = 1020)

Notable inorganic iodine compounds

See also iodine compounds

Stable iodine in biology

Iodine is an essential trace element; its only known roles in biology are as constituents of the thyroid hormones, thyroxine (T4) and triiodothyronine (T3). These are made from addition condensation products of the amino acid tyrosine, and are stored prior to release in a protein-like molecule called thryroglobulin. T4 and T3 contain four and three atoms of iodine per molecule, respectively. The thyroid gland actively absorbs iodide from the blood to make and release these hormones into the blood, actions which are regulated by a second hormone TSH from the pituitary. Thyroid hormones are phylogenetically very old molecules which are synthesized by most multicellular organisms, and which even have some effect on unicellular organisms.

Thyroid hormones play a very basic role in biology, acting on gene transcription to regulate the basal metabolic rate. The total deficiency of thyroid hormones can reduce basal metabolic rate up to 50%, while in excessive production of thyroid hormones the basal metabolic rate can be increased by 100%. T4 acts largely as a precursor to T3, which is (with some minor exceptions) the biologically active hormone.

Human dietary intake

The United States Food and Drug Administration recommends 150 micrograms of iodine per day for both men and women.^[6] This is necessary for proper production of thyroid hormone.^{[citation needed]} Natural sources of iodine include sea life, such as kelp and certain seafood, as well as plants grown on iodine-rich soil.^{[citation needed]} Salt for human consumption is often fortified with iodine and is referred to as iodized salt.

Iodine deficiency

Main article: Iodine deficiency

In areas where there is little iodine in the diet—typically remote inland areas and semi-arid equatorial climates where no marine foods are eaten—iodine deficiency gives rise to hypothyroidism, symptoms of which are extreme fatigue, goitre, mental slowing, depression, weight gain, and low basal body temperatures.^{[citation needed]}

Iodine deficiency is also the leading cause of preventable mental retardation, an effect which happens primarily when babies and small children are made hypothyroid by lack of the element. The addition of iodine to table salt has largely eliminated this problem in the wealthier nations, but iodine deficiency remains a serious public health problem in the developing world.^{[citation needed]}

Radioiodine and biology

Radioiodine and the thyroid

The artificial radioisotope ¹³¹I (a beta emitter), also known as radioiodine which has a half-life of 8.0207 days, has been used in treating cancer and other pathologies of the thyroid glands. ¹²³I is the radioisotope most often used in nuclear imaging of the kidney and thyroid as well as thyroid uptake scans (used for the evaluation of Graves' Disease). The most common compounds of iodine are the iodides of sodium and potassium (KI) and the iodates (KIO₃).

¹²⁹I (half-life 15.7 million years) is a product of ¹³⁰Xe spallation in the atmosphere and uranium and plutonium fission, both in subsurface rocks and nuclear reactors. Nuclear processes, in particular nuclear fuel reprocessing and atmospheric nuclear weapons tests have now swamped the natural signal for this isotope. ¹²⁹I was used in rainwater studies following the Chernobyl accident. It also has been used as a ground-water tracer and as an indicator of nuclear waste dispersion into the natural environment.

If humans are exposed to radioactive iodine, the thyroid gland will absorb it as if it were non-radioactive iodine, leading to elevated chances of thyroid cancer. Isotopes with shorter half-lives such as ¹³¹I present a greater risk than those with longer half-lives since they generate more radiation per unit of time. Taking large amounts of regular iodine will saturate the thyroid and prevent uptake. Iodine pills are sometimes distributed to persons living close to nuclear establishments, for use in case of accidents that could lead to releases of radioactive iodine.

• Iodine-123 and iodine-125 are used in medicine as tracers for imaging and evaluating the function of the thyroid.
• Iodine-131 is used in medicine for treatment of thyroid cancer and Graves' Disease.
• Uncombined (elemental) iodine is mildly toxic to all living things.
• Potassium iodide (KI tablets, or "SSKI" = "Saturated Solution of KI" liquid drops) can be given to people in a nuclear disaster area when fission has taken place, to flush out the radioactive iodine-131 fission product. The half-life of iodine-131 is only eight days, so the treatment would need to continue only a couple of weeks. In cases of leakage of certain nuclear materials without fission, or certain types of dirty bomb made with other than radioiodine, this precaution would be of no avail.

Radioiodine and the kidney

In the 1970s imaging techniques were developed in California to utilize radioiodine in diagnostics for renal hypertension.

Isotopes

Main article: isotopes of iodine

There are 37 isotopes of iodine and only one, ¹²⁷I, is stable.

In many ways, ¹²⁹I is similar to ³⁶Cl. It is a soluble halogen, fairly non-reactive, exists mainly as a non-sorbing anion, and is produced by cosmogenic, thermonuclear, and in-situ reactions. In hydrologic studies, ¹²⁹I concentrations are usually reported as the ratio of ¹²⁹I to total I (which is virtually all ¹²⁷I). As is the case with ³⁶Cl/Cl, ¹²⁹I/I ratios in nature are quite small, 10⁻¹⁴ to 10⁻¹⁰ (peak thermonuclear ¹²⁹I/I during the 1960s and 1970s reached about 10⁻⁷). ¹²⁹I differs from ³⁶Cl in that its half-life is longer (15.7 vs. 0.301 million years), it is highly biophilic, and occurs in multiple ionic forms (commonly, I⁻ and IO₃⁻) which have different chemical behaviors. This makes it fairly easy for ¹²⁹I to enter the biosphere as it becomes incorporated into vegetation, soil, milk, animal tissue, etc.

Excesses of stable ¹²⁹Xe in meteorites have been shown to result from decay of "primordial" ¹²⁹I produced newly by the supernovas which created the dust and gas from which the solar system formed. ¹²⁹I was the first extinct radionuclide to be identified as present in the early solar system. Its decay is the basis of the I-Xe radiometric dating scheme, which covers the first 83 million years of solar system evolution.

Effects of various radioiodine isotopes in biology are discussed below.

Toxicity of iodine

Excess iodine has symptoms similar to those of iodine deficiency. Commonly encountered symptoms are abnormal growth of the thyroid gland and disorders in functioning and growth of the organism as a whole. Elemental iodine, I₂, is a deadly poison if taken in larger amounts; if 2-3 grams of it is consumed, it is fatal to humans. Iodides are similar in toxicity to bromides.

Precautions for stable iodine

Direct contact with skin can cause lesions, so it should be handled with care. Iodine vapor is very irritating to the eye and to mucous membranes. Concentration of iodine in the air should not exceed 1 mg/m³ (eight-hour time-weighted average). When mixed with ammonia, it can form nitrogen triiodide which is extremely sensitive and can explode unexpectedly.

Clandestine use

In the United States, the Drug Enforcement Agency (DEA) regards iodine and compounds containing iodine (ionic iodides, iodoform, ethyl iodide, and so on) as reagents useful for the clandestine manufacture of methamphetamine. Persons who attempt to purchase significant quantities of such chemicals without establishing a legitimate use are likely to find themselves the target of a DEA investigation. Persons selling such compounds without doing due diligence to establish that the materials are not being diverted to clandestine use may be subject to stiff penalties, such as expensive fines or even imprisonment.^[7][8]

See also

• Iodide as an antioxidant
• Iodised salt
• Chemical Oxygen Iodine Laser

References

1. ^ DNSC, 2006
2. ^ ^{a b c} Advanced Inorganic Chemistry by Cotton and Wilkinson, 2nd ed.
3. ^ Merck Index of Chemicals and Drugs, 9th ed.
4. ^ General Chemistry (volume 2) by N.L. Glinka, Mir Publishing 1981
5. ^ ^{a b} General Chemistry by Linus Pauling, 1947 ed.
6. ^ 21 CFR 101.9 (c)(8)(iv)
7. ^ 21 USC Sec. 872 01/22/02
8. ^ Chemical Supplier Convicted of Diversion of Iodine