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The halogens (

(2025). 9783125396838, Cambridge University Press.
) are a group in the consisting of six chemically related : (F), (Cl), (Br), (I), and the elements (At) and (Ts), though some authors Fricke, Burkhard 2007.12.?? Superheavy elements a prediction of their chemical and physical properties PDF | "Element 117" | www.researchgate.net | Retrieved - 2023.08.13 (20:58:??) -- yyyy.mm.dd (hh:mm:ss) would exclude tennessine as its chemistry is unknown and is theoretically expected to be more like that of . In the modern nomenclature, this group is known as group 17.
(2025). 9780854044382, Royal Society of Chemistry.

The word "halogen" means "salt former" or "salt maker". When halogens react with , they produce a wide range of salts, including , (common table salt), and .

The group of halogens is the only periodic table group that contains elements in three of the main states of matter at standard temperature and pressure, though not far above room temperature the same becomes true of groups and , assuming white phosphorus is taken as the standard state.This could also be the case for group 12, although 's melting and boiling points are still uncertain. All of the halogens form acids when bonded to hydrogen. Most halogens are typically produced from or salts. The middle halogens—chlorine, bromine, and iodine—are often used as . Organobromides are the most important class of , while elemental halogens are dangerous and can be toxic.


History
The fluorine mineral was known as early as 1529. It is believed to be found in the foot bones of early dinosaurs. Early chemists realized that fluorine compounds contain an undiscovered element, but were unable to isolate it. In 1860, George Gore, an English chemist, ran a current of electricity through hydrofluoric acid and probably produced fluorine, but he was unable to prove his results at the time. In 1886, , a chemist in Paris, performed on potassium bifluoride dissolved in anhydrous hydrogen fluoride, and successfully isolated fluorine.
(2025). 9780199605637, OUP Oxford.

Hydrochloric acid was known to and early chemists. However, elemental chlorine was not produced until 1774, when Carl Wilhelm Scheele heated hydrochloric acid with manganese dioxide. Scheele called the element "dephlogisticated muriatic acid", which is how chlorine was known for 33 years. In 1807, investigated chlorine and discovered that it is an actual element. Chlorine gas was used as a during World War I. It displaced oxygen in contaminated areas and replaced common oxygenated air with the toxic chlorine gas. The gas would burn human tissue externally and internally, especially the lungs, making breathing difficult or impossible depending on the level of contamination.

Bromine was discovered in the 1820s by Antoine Jérôme Balard. Balard discovered bromine by passing chlorine gas through a sample of . He originally proposed the name muride for the new element, but the changed the element's name to bromine.

Iodine was discovered by , who was using ash as part of a process for manufacture. Courtois typically boiled the seaweed ash with water to generate potassium chloride. However, in 1811, Courtois added sulfuric acid to his process and found that his process produced purple fumes that condensed into black crystals. Suspecting that these crystals were a new element, Courtois sent samples to other chemists for investigation. Iodine was proven to be a new element by Joseph Gay-Lussac.

In 1931, claimed to have discovered element 85 with a magneto-optical machine, and named the element Alabamine, but was mistaken. In 1937, claimed to have discovered element 85 in minerals, and called the element dakine, but he was also mistaken. An attempt at discovering element 85 in 1939 by and via was also unsuccessful, as was an attempt in the same year by , who discovered an iodine-like element resulting from of . Element 85, now named , was produced successfully in 1940 by Dale R. Corson, K.R. Mackenzie, and Emilio G. Segrè, who bombarded with .

In 2010, a team led by nuclear physicist involving scientists from the , Oak Ridge National Laboratory, Lawrence Livermore National Laboratory, and Vanderbilt University successfully bombarded berkelium-249 atoms with calcium-48 atoms to make tennessine.


Etymology
In 1811, the German chemist Johann Schweigger proposed that the name "halogen" – meaning "salt producer", from αλς hals "salt" and γενειν genein "to beget" – replace the name "chlorine", which had been proposed by the English chemist . On p. 251, Schweigger proposed the word "halogen": "Man sage dafür lieber mit richter Wortbildung Halogen (da schon in der Mineralogie durch Werner's Halit-Geschlecht dieses Wort nicht fremd ist) von αλς Salz und dem alten γενειν (dorisch γενεν) zeugen ." (One should say instead, with proper morphology, "halogen" (this word is not strange since it's already in mineralogy via Werner's "halite" species) from αλς als "salt" and the old γενειν genein (Doric γενεν) "to beget".) Davy's name for the element prevailed. However, in 1826, the Baron Jöns Jacob Berzelius proposed the term "halogen" for the elements fluorine, chlorine, and iodine, which produce a sea-salt-like substance when they form a compound with an alkaline metal.In 1826, Berzelius coined the terms Saltbildare (salt-formers) and Corpora Halogenia (salt-making substances) for the elements chlorine, iodine, and fluorine. See: From p. 187: "De förre af dessa, d. ä. de electronegativa , dela sig i tre klasser: 1) den första innehåller kroppar, som förenade med de electropositiva, omedelbart frambringa salter, hvilka jag derför kallar Saltbildare (Corpora Halogenia). Desse utgöras af chlor, iod och fluor *)." (The first of them i.e.,, the electronegative ones, are divided into three classes: 1) The first includes substances which, when united with electropositive elements, immediately produce salts, and which I therefore name "salt-formers" (salt-producing substances). These are chlorine, iodine, and fluorine *).)The word "halogen" appeared in English as early as 1832 (or earlier). See, for example: Berzelius, J.J. with A.D. Bache, trans., (1832) "An essay on chemical nomenclature, prefixed to the treatise on chemistry," The American Journal of Science and Arts, 22: 248–276 ; see, for example p. 263.

The English names of these elements all have the ending . Fluorine's name comes from the word fluere, meaning "to flow", because it was derived from the mineral , which was used as a flux in metalworking. Chlorine's name comes from the word chloros, meaning "greenish-yellow". Bromine's name comes from the Greek word bromos, meaning "stench". Iodine's name comes from the Greek word iodes, meaning "violet". Astatine's name comes from the Greek word astatos, meaning "unstable". Tennessine is named after the US state of , where it was synthesized.


Characteristics

Chemical
The halogens fluorine, chlorine, bromine, and iodine are nonmetals; the chemical properties of astatine and tennessine, two heaviest group 17 members, have not been conclusively investigated. The halogens show trends in chemical bond energy moving from top to bottom of the periodic table column with fluorine deviating slightly. It follows a trend in having the highest bond energy in compounds with other atoms, but it has very weak bonds within the diatomic F2 molecule. This means that further down group 17 in the periodic table, the reactivity of elements decreases because of the increasing size of the atoms.Page 43, Edexcel International GCSE chemistry revision guide, Curtis 2011

Halogen bond energies (kJ/mol)

Halogens are highly reactive, and as such can be harmful or lethal to in sufficient quantities. This high reactivity is due to the high electronegativity of the atoms due to their high effective nuclear charge. Because the halogens have seven valence electrons in their outermost energy level, they can gain an electron by reacting with atoms of other elements to satisfy the . is the most reactive of all elements; it is the only element more electronegative than oxygen, it attacks otherwise-inert materials such as glass, and it forms compounds with the usually inert . It is a corrosive and highly toxic gas. The reactivity of fluorine is such that, if used or stored in laboratory glassware, it can react with glass in the presence of small amounts of water to form silicon tetrafluoride (SiF4). Thus, fluorine must be handled with substances such as Teflon (which is itself an compound), extremely dry glass, or metals such as copper or steel, which form a protective layer of fluoride on their surface.

The high reactivity of fluorine allows some of the strongest bonds possible, especially to carbon. For example, Teflon is fluorine bonded with carbon and is extremely resistant to thermal and chemical attacks and has a high melting point.


Molecules

Diatomic halogen molecules
The stable halogens form . Due to relatively weak intermolecular forces, chlorine and fluorine form part of the group known as "elemental gases".

149
198
227
272

The elements become less reactive and have higher melting points as the atomic number increases. The higher melting points are caused by stronger London dispersion forces resulting from more electrons.


Compounds

Hydrogen halides
All of the halogens have been observed to react with hydrogen to form . For fluorine, chlorine, and bromine, this reaction is in the form of:

H2 + X2 → 2HX

However, hydrogen iodide and hydrogen astatide can split back into their constituent elements.

The hydrogen-halogen reactions get gradually less reactive toward the heavier halogens. A fluorine-hydrogen reaction is explosive even when it is dark and cold. A chlorine-hydrogen reaction is also explosive, but only in the presence of light and heat. A bromine-hydrogen reaction is even less explosive; it is explosive only when exposed to flames. Iodine and astatine only partially react with hydrogen, forming equilibria.

All halogens form binary compounds with hydrogen known as the hydrogen halides: hydrogen fluoride (HF), hydrogen chloride (HCl), (HBr), (HI), and hydrogen astatide (HAt). All of these compounds form acids when mixed with water. Hydrogen fluoride is the only hydrogen halide that forms . Hydrochloric acid, hydrobromic acid, hydroiodic acid, and acid are all , but hydrofluoric acid is a .

All of the hydrogen halides are . Hydrogen fluoride and hydrogen chloride are highly . Hydrogen fluoride is used as an indu chemical, and is highly toxic, causing and damaging cells. Hydrogen chloride is also a dangerous chemical. Breathing in gas with more than fifty parts per million of hydrogen chloride can cause death in humans. Hydrogen bromide is even more toxic and irritating than hydrogen chloride. Breathing in gas with more than thirty parts per million of hydrogen bromide can be lethal to humans. Hydrogen iodide, like other hydrogen halides, is toxic.


Metal halides
All the halogens are known to react with sodium to form , , , , and sodium astatide. Heated sodium's reaction with halogens produces bright-orange flames. Sodium's reaction with chlorine is in the form of:

Iron reacts with fluorine, chlorine, and bromine to form iron(III) halides. These reactions are in the form of:

However, when iron reacts with iodine, it forms only iron(II) iodide.

Iron wool can react rapidly with fluorine to form the white compound iron(III) fluoride even in cold temperatures. When chlorine comes into contact with a heated iron, they react to form the black iron(III) chloride. However, if the reaction conditions are moist, this reaction will instead result in a reddish-brown product. Iron can also react with bromine to form iron(III) bromide. This compound is reddish-brown in dry conditions. Iron's reaction with bromine is less reactive than its reaction with fluorine or chlorine. A hot iron can also react with iodine, but it forms iron(II) iodide. This compound may be gray, but the reaction is always contaminated with excess iodine, so it is not known for sure. Iron's reaction with iodine is less vigorous than its reaction with the lighter halogens.


Interhalogen compounds
Interhalogen compounds are in the form of XYn where X and Y are halogens and n is one, three, five, or seven. Interhalogen compounds contain at most two different halogens. Large interhalogens, such as can be produced by a reaction of a pure halogen with a smaller interhalogen such as . All interhalogens except can be produced by directly combining pure halogens in various conditions.
(2025). 9788183562430, Discovery Publishing House. .

Interhalogens are typically more reactive than all diatomic halogen molecules except F2 because interhalogen bonds are weaker. However, the chemical properties of interhalogens are still roughly the same as those of halogens. Many interhalogens consist of one or more atoms of fluorine bonding to a heavier halogen. Chlorine and bromine can bond with up to five fluorine atoms, and iodine can bond with up to seven fluorine atoms. Most interhalogen compounds are gases. However, some interhalogens are liquids, such as BrF3, and many iodine-containing interhalogens are solids.


Organohalogen compounds
Many synthetic organic compounds such as , and a few natural ones, contain halogen atoms; these are known as halogenated compounds or . Chlorine is by far the most abundant of the halogens in seawater, and the only one needed in relatively large amounts (as chloride ions) by humans. For example, chloride ions play a key role in function by mediating the action of the inhibitory transmitter GABA and are also used by the body to produce stomach acid. Iodine is needed in trace amounts for the production of hormones such as . Organohalogens are also synthesized through the nucleophilic abstraction reaction.
(2025). 9783211993224, Springer. .


Polyhalogenated compounds
Polyhalogenated compounds are industrially created compounds substituted with multiple halogens. Many of them are very toxic and bioaccumulate in humans, and have a very wide application range. They include PCBs, , and perfluorinated compounds (PFCs), as well as numerous other compounds.


Reactions

Reactions with water
Fluorine reacts vigorously with water to produce (O2) and hydrogen fluoride (HF):

Chlorine has maximum solubility of ca. 7.1 g Cl2 per kg of water at ambient temperature (21 °C). Dissolved chlorine reacts to form hydrochloric acid (HCl) and hypochlorous acid, a solution that can be used as a or :

Bromine has a solubility of 3.41 g per 100 g of water, but it slowly reacts to form (HBr) and (HBrO):

Iodine, however, is minimally soluble in water (0.03 g/100 g water at 20 °C) and does not react with it. However, iodine will form an aqueous solution in the presence of iodide ion, such as by addition of (KI), because the ion is formed.


Physical and atomic
The table below is a summary of the key physical and atomic properties of the halogens. Data marked with question marks are either uncertain or are estimations partially based on rather than observations.

71
99
114
133
? 145
? 157

2, 7
2, 8, 7
2, 8, 18, 7
2, 8, 18, 18, 7
2, 8, 18, 32, 18, 7
2, 8, 18, 32, 32, 18, 7 (predicted)
(2025). 9789400702103, Springer Science+Business Media.
+Sublimation or boiling point (oC) of halogens at various pressuresTmelt (оС)−100.7−7.3112.9
2.124903021−118−48.738.7
2.823873025−106.7−32.862.2
3.1249030210−101.6−2573.2
3.4259330220−93.3−16.884.7
3.7269630140−84.5−897.5
3.9030542760−79−0.6105.4
4.12490302100−71.79.3116.5
4.42593302200−60.224.3137.3
4.72696301400−47.341159.8
5.00571661760−33.858.2183
5.005716611−33.858.2183
5.306746612−16.978.8
5.70468662510.3110.3
6.005716611035.6139.8
6.306746612065174
6.482837873084.8197
6.607776640101.6215
6.7046866250115.2230
6.7838678660127.1243.5


Isotopes
Fluorine has one stable and naturally occurring isotope, fluorine-19. However, there are trace amounts in nature of the radioactive isotope fluorine-23, which occurs via of protactinium-231. A total of eighteen isotopes of fluorine have been discovered, with atomic masses ranging from 13 to 31.

Chlorine has two stable and naturally occurring isotopes, chlorine-35 and chlorine-37. However, there are trace amounts in nature of the isotope chlorine-36, which occurs via of argon-36. A total of 24 isotopes of chlorine have been discovered, with atomic masses ranging from 28 to 51.

There are two stable and naturally occurring isotopes of bromine, bromine-79 and bromine-81. A total of 33 isotopes of bromine have been discovered, with atomic masses ranging from 66 to 98.

There is one stable and naturally occurring isotope of iodine, iodine-127. However, there are trace amounts in nature of the radioactive isotope iodine-129, which occurs via spallation and from the radioactive decay of uranium in ores. Several other radioactive isotopes of iodine have also been created naturally via the decay of uranium. A total of 38 isotopes of iodine have been discovered, with atomic masses ranging from 108 to 145.

There are no stable isotopes of astatine. However, there are four naturally occurring radioactive isotopes of astatine produced via radioactive decay of , , and . These isotopes are astatine-215, astatine-217, astatine-218, and astatine-219. A total of 31 isotopes of astatine have been discovered, with atomic masses ranging from 191 to 227.

There are no stable isotopes of tennessine. Tennessine has only two known synthetic radioisotopes, tennessine-293 and tennessine-294.


Production
Approximately six million metric tons of the fluorine mineral are produced each year. Four hundred-thousand metric tons of hydrofluoric acid are made each year. Fluorine gas is made from hydrofluoric acid produced as a by-product in manufacture. Approximately 15,000 metric tons of fluorine gas are made per year.

The mineral is the mineral that is most commonly mined for chlorine, but the minerals and are also mined for chlorine. Forty million metric tons of chlorine are produced each year by the of .

Approximately 450,000 metric tons of bromine are produced each year. Fifty percent of all bromine produced is produced in the , 35% in , and most of the remainder in . Historically, bromine was produced by adding and bleaching powder to natural brine. However, in modern times, bromine is produced by electrolysis, a method invented by . It is also possible to produce bromine by passing chlorine through seawater and then passing air through the seawater.

In 2003, 22,000 metric tons of iodine were produced. Chile produces 40% of all iodine produced, produces 30%, and smaller amounts are produced in and the United States. Until the 1950s, iodine was extracted from . However, in modern times, iodine is produced in other ways. One way that iodine is produced is by mixing with ores, which contain some . Iodine is also extracted from fields.

Even though astatine is naturally occurring, it is usually produced by bombarding bismuth with alpha particles.

Tennessine is made by using a cyclotron, fusing berkelium-249 and calcium-48 to make tennessine-293 and tennessine-294.


Applications

Disinfectants
Both chlorine and bromine are used as for drinking water, swimming pools, fresh wounds, spas, dishes, and surfaces. They kill and other potentially harmful through a process known as sterilization. Their reactivity is also put to use in . Sodium hypochlorite, which is produced from chlorine, is the active ingredient of most bleaches, and chlorine-derived bleaches are used in the production of some products.


Lighting
are a type of incandescent lamp using a filament in bulbs that have small amounts of a halogen, such as iodine or bromine added. This enables the production of lamps that are much smaller than non-halogen incandescent lightbulbs at the same . The gas reduces the thinning of the filament and blackening of the inside of the bulb resulting in a bulb that has a much greater life. Halogen lamps glow at a higher temperature (2800 to 3400 ) with a whiter colour than other incandescent bulbs. However, this requires bulbs to be manufactured from rather than silica glass to reduce breakage.


Drug components
In , the incorporation of halogen atoms into a lead drug candidate results in analogues that are usually more and less water-soluble.
(2025). 9780470025970, John Wiley & Sons, West Sussex, UK.
As a consequence, halogen atoms are used to improve penetration through and tissues. It follows that there is a tendency for some halogenated drugs to accumulate in .

The chemical reactivity of halogen atoms depends on both their point of attachment to the lead and the nature of the halogen. halogen groups are far less reactive than halogen groups, which can exhibit considerable chemical reactivity. For aliphatic carbon-halogen bonds, the C-F bond is the strongest and usually less chemically reactive than aliphatic C-H bonds. The other aliphatic-halogen bonds are weaker, their reactivity increasing down the periodic table. They are usually more chemically reactive than aliphatic C-H bonds. As a consequence, the most common halogen substitutions are the less reactive aromatic fluorine and chlorine groups.


Biological role
Fluoride anions are found in ivory, bones, teeth, blood, eggs, urine, and hair of organisms. Fluoride anions in very small amounts may be essential for humans. There are 0.5 milligrams of fluorine per liter of human blood. Human bones contain 0.2 to 1.2% fluorine. Human tissue contains approximately 50 parts per billion of fluorine. A typical 70-kilogram human contains 3 to 6 grams of fluorine.

Chloride anions are essential to a large number of species, humans included. The concentration of chlorine in the of cereals is 10 to 20 parts per million, while in the concentration of chloride is 0.5%. Plant growth is adversely affected by chloride levels in the falling below 2 parts per million. Human blood contains an average of 0.3% chlorine. Human bone typically contains 900 parts per million of chlorine. Human tissue contains approximately 0.2 to 0.5% chlorine. There is a total of 95 grams of chlorine in a typical 70-kilogram human.

Some bromine in the form of the bromide anion is present in all organisms. A biological role for bromine in humans has not been proven, but some organisms contain organobromine compounds. Humans typically consume 1 to 20 milligrams of bromine per day. There are typically 5 parts per million of bromine in human blood, 7 parts per million of bromine in human bones, and 7 parts per million of bromine in human tissue. A typical 70-kilogram human contains 260 milligrams of bromine.

Humans typically consume less than 100 micrograms of iodine per day. Iodine deficiency can cause intellectual disability. Organoiodine compounds occur in humans in some of the , especially the , as well as the , epidermis, and . Foods containing iodine include cod, , shrimp, herring, , , , and . However, iodine is not known to have a biological role in plants. There are typically 0.06 milligrams per liter of iodine in human blood, 300 parts per billion of iodine in human bones, and 50 to 700 parts per billion of iodine in human tissue. There are 10 to 20 milligrams of iodine in a typical 70-kilogram human.

, although very scarce, has been found in micrograms in the earth. It has no known biological role because of its high radioactivity, extreme rarity, and has a half-life of just about 8 hours for the most stable isotope.

Tennessine is purely man-made and has no other roles in nature.


Toxicity
The halogens tend to decrease in toxicity towards the heavier halogens.

Fluorine gas is extremely toxic; breathing in fluorine at a concentration of 25 parts per million is potentially lethal. Hydrofluoric acid is also toxic, being able to penetrate skin and cause highly painful burns. In addition, fluoride anions are toxic, but not as toxic as pure fluorine. Fluoride can be lethal in amounts of 5 to 10 grams. Prolonged consumption of fluoride above concentrations of 1.5 mg/L is associated with a risk of , an aesthetic condition of the teeth.

(2025). 9789241563192, World Health Organization.
At concentrations above 4 mg/L, there is an increased risk of developing skeletal fluorosis, a condition in which bone fractures become more common due to the hardening of bones. Current recommended levels in water fluoridation, a way to prevent , range from 0.7 to 1.2 mg/L to avoid the detrimental effects of fluoride while at the same time reaping the benefits. People with levels between normal levels and those required for skeletal fluorosis tend to have symptoms similar to .

Chlorine gas is highly toxic. Breathing in chlorine at a concentration of 3 parts per million can rapidly cause a toxic reaction. Breathing in chlorine at a concentration of 50 parts per million is highly dangerous. Breathing in chlorine at a concentration of 500 parts per million for a few minutes is lethal. In addition, breathing in chlorine gas is highly painful because of its corrosive properties. Hydrochloric acid is the acid of chlorine, while relatively nontoxic, it is highly corrosive and releases very irritating and toxic hydrogen chloride gas in open air.

(2025). 9781579128951, Running Press.

Pure bromine is somewhat toxic but less toxic than fluorine and chlorine. One hundred milligrams of bromine is lethal. Bromide anions are also toxic, but less so than bromine. Bromide has a lethal dose of 30 grams.

Iodine is somewhat toxic, being able to irritate the lungs and eyes, with a safety limit of 1 milligram per cubic meter. When taken orally, 3 grams of iodine can be lethal. Iodide anions are mostly nontoxic, but these can also be deadly if ingested in large amounts.

Astatine is and thus highly dangerous, but it has not been produced in macroscopic quantities and hence it is most unlikely that its toxicity will be of much relevance to the average individual.

Tennessine cannot be chemically investigated due to how short its half-life is, although its radioactivity would make it very dangerous.


Superhalogen
Certain aluminium clusters have superatom properties. These aluminium clusters are generated as anions ( with n = 1, 2, 3, ... ) in helium gas and reacted with a gas containing iodine. When analyzed by mass spectrometry one main reaction product turns out to be . These clusters of 13 aluminium atoms with an extra electron added do not appear to react with oxygen when it is introduced in the same gas stream. Assuming each atom liberates its 3 valence electrons, this means 40 electrons are present, which is one of the magic numbers for sodium and implies that these numbers are a reflection of the noble gases.

Calculations show that the additional electron is located in the aluminium cluster at the location directly opposite from the iodine atom. The cluster must therefore have a higher electron affinity for the electron than iodine and therefore the aluminium cluster is called a superhalogen (i.e., the vertical electron detachment energies of the moieties that make up the negative ions are larger than those of any halogen atom). The cluster component in the ion is similar to an iodide ion or a bromide ion. The related cluster is expected to behave chemically like the ion.


See also


Notes

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