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GROUP 7

Halogen The of is the only group that contains elements in all three familiar states of matter at standard temperature and pressure. All of the halogens form when bonded to . Most halogens are typically produced from minerals of salts. The middle halogens, that is, , and , are often used as disinfectants. The halogens are also all toxic. Characteristics Chemical The halogens show trends in chemical bond energy moving from top to bottom of the periodic table column with deviating slightly. (It follows trend in having the highest bond energy in compounds with other , but it has very weak bonds within the diatomic F2 element .) bond energies (kJ/mol)[4]

X X2 HX BX3 AlX3 CX4 F 159 574 645 582 456 Cl 243 428 444 427 327 Br 193 363 368 360 272

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I 151 294 272 285 239 Halogens are highly reactive, and as such can be harmful or lethal to biological organisms in sufficient quantities. This high reactivity is due to the high of the atoms due to their high effective nuclear charge. They can gain an electron by reacting with atoms of other elements. Fluorine is one of the most reactive elements in existence, attacking otherwise-inert materials such as glass, and forming compounds with the heavier noble gases. 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 to form tetrafluoride (SiF4). Thus, fluorine must be handled with substances such as Teflon (which is itself an organofluorine compound), extremely dry glass, or such as or steel, which form a protective layer of fluoride on their surface. The high reactivity of fluorine means that, once it does react with something, it bonds with it so strongly that the resulting is very inert and non-reactive to anything else. For example, Teflon is fluorine bonded with . Molecules Diatomic halogen molecules

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The halogens form homonuclear diatomic molecules (not proven for ). As such they form part of the group known as "elemental gases".

d(X−X) / d(X−X) / pm pm halogen molecule structure model (gas (solid phase) phase)

fluorine F2 143 149

chlorine Cl2 199 198

bromine Br2 228 227

iodine I2 266 272

astatine At2

The elements become less reactive and have higher melting points as the atomic number increases. Compounds Hydrogen

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

H2 + X2 → 2HX However, and hydrogen astatide can split back into their constituent elements.[5] 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.[5] All halogens form binary compounds with hydrogen known as the hydrogen halides: (HF), hydrogen (HCl), (HBr), hydrogen iodide (HI), and hydrogen astatide (HAt). All of these compounds form acids when mixed with water. Hydrogen fluoride is the only hydrogen that forms hydrogen bonds. Hydrochloric , , , and hydroastatic acid are all strong acids, but hydrofluoric acid is a weak acid.[6] All of the hydrogen halides are irritants. Hydrogen fluoride and are highly acidic.

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Hydrogen fluoride is used as an industrial chemical, and is highly toxic, causing pulmonary edema and damaging cells.[7] 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.[8] 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.[9] Hydrogen iodide, like other hydrogen halides, is toxic.[10] halides Main article: Metal halides All the halogens are known to react with to form , , sodium bromide, sodium iodide, and sodium astatide. Heated sodium's reaction with halogens produces bright-orange flames. Sodium's reaction with chlorine is in the form of:

[5] 2Na + Cl2 → 2NaCl reacts with fluorine, chlorine, and bromine to form Iron(III) halides. These reactions are in the form of:

[5] 2Fe + 3X2 → 2FeX3 However, when iron reacts with iodine, it forms only iron(II) iodide.

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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 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. 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.[5] compounds Main article: Interhalogen

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 , such as ClF3 can be produced by a reaction of a pure halogen with a smaller interhalogen such as ClF. All interhalogens except IF7 can be produced by directly combining pure halogens in various conditions.[11]

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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 diatomic halogens. Many interhalogens consist of one or more atoms of fluorine bonding to a heavier halogen. Chlorine can bond with up to 3 fluorine atoms, bromine can bond with up to five fluorine atoms, and iodine can bond with up to seven fluorine atoms. Most interhalogen compounds are covalent gases. However, there are some interhalogens that are , such as BrF3, and many iodine-containing interhalogens are solids.[11] Organohalogen compounds Many synthetic organic compounds such as polymers, and a few natural ones, contain halogen atoms; these are known as halogenated compounds or organic halides. Chlorine is by far the most abundant of the halogens, and the only one needed in relatively large amounts (as chloride ) by humans. For example, chloride ions play a key role in brain 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 thyroid hormones such as thyroxine. On the other hand, neither fluorine nor bromine is believed to be essential for

7 humans. Organohalogens are also synthesized through the nucleophilic abstraction reaction. 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 the much-maligned PCBs, PBDEs, and perfluorinated compounds (PFCs), as well as numerous other compounds. Reactions Reactions with water Fluorine reacts vigorously with water to produce [12] (O2) and hydrogen fluoride (HF):

2 F2(g) + 2 H2O(l) → O2(g) + 4 HF(aq)

Chlorine has maximum solubility of ca. 7.1 g Cl2 per kg of water at ambient temperature (21 °C).[13] Dissolved chlorine reacts to form (HCl) and , a that can be used as a disinfectant or bleach:

Cl2(g) + H2O(l) → HCl(aq) + HClO(aq)

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Bromine has a solubility of 3.41 g per 100 g of water,[14] but it slowly reacts to form hydrogen bromide (HBr) and (HBrO):

Br2(g) + H2O(l) → HBr(aq) + HBrO(aq) Iodine, however, is minimally soluble in water (0.03 g/100 g water at 20 °C) and does not react with it.[15] However, iodine will form an aqueous solution in the presence of iodide , such as by addition of iodide (KI), because the triiodide 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 periodic trends rather than observations. First Cov Standa Mel Boi Boil Den ioniz Mel alen rd ting ling ing sity Electron ation Hal ting t atomic poi poi poi (g/c egativity ener oge poi radi weight nt nt nt m3a (Pauling gy n nt us (u)[n (°C (K) (°C t 25 ) (kJ· (K) (pm 1][17] ) [18] )[18] °C) mol−1 )[19] ) Fluo 18.998 53.5 −21 85. −18 0.00 3.98 1681. 71

9 rine 4032(5 3 9.62 03 8.12 17 0 ) [35.446 Chl ; 171. −10 239 −34 0.00 1251. orin 3.16 99 35.457] 6 1.5 .11 .04 32 2

e [n 2] Bro 79.904( 265. −7. 332 3.10 1139. min 58.8 2.96 114 1) 8 3 .0 28 9

e Iodi 126.90 386. 113. 457 184. 4.93 1008. 2.66 133

ne 447(3) 85 7 .4 3 3 4 ? Asta [210][n ? ? 6.2– ? 3] 575 302 [2 2.2 ? tine 610 337 6.5 887.7 0] Fluorine has one stable and naturally occurring , fluorine-19. However, there are trace amounts in nature of the radioactive isotope fluorine-23, which occurs via cluster decay of -231. A total of eighteen have been discovered, with atomic masses ranging from 14 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

10 -36. A total of 24 have been discovered, with atomic masses ranging from 28 to 51.[1] There are two stable and naturally occurring , bromine-79 and bromine-81. A total of 32 isotopes of bromine have been discovered, with atomic masses ranging 67 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 of in ores. Several other radioactive 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.[1] There are no stable . However, there are three naturally occurring radioactive isotopes of astatine produced via radioactive decay of uranium, , and . These isotopes are astatine- 215, astatine-217, and astatine-219. A total of 31 isotopes of astatine have been discovered, with atomic masses ranging from 193 to 223.[1] 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

11 year. Fluorine gas is made from hydrofluoric acid produced as a by-product of manufacture. Approximately 15,000 metric tons of fluorine gas are made per year.[1] The mineral halite is the mineral that is most commonly mined for chlorine, but the minerals carnallite and sylvite are also mined for chlorine. Forty million metric tons of chlorine are produced each year by the electrolysis of brine.[1] Approximately 450,000 metric tons of bromine are produced each year. Fifty percent of all bromine produced is produced in the United States, 35% in Israel, and most of the remainder in China. 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 Herbert Dow. It is also possible to produce bromine by passing chlorine through and then passing air through the seawater.[1] In 2003, 22,000 metric tons of iodine were produced. Chile produces 40% of all iodine produced, Japan produces 30%, and smaller amonts are produced in Russia and the United States. Until the 1950s, iodine was extracted from kelp. However, in modern times, iodine is produced in other ways. One way that iodine is produced is by mixing dioxide with nitrate ores, which

12 contain some iodates. Iodine is also extracted from natural gas fields.[1] Even though astatine is naturally occurring, it is usually produced by bombarding with alpha particles.[1]

From left to right: chlorine, bromine, and iodine at room temperature. Chlorine is a gas, bromine is a , and iodine is a solid. Fluorine could not be included in the image due to its high reactivity. Applications Both chlorine and bromine are used as disinfectants for drinking water, swimming pools, fresh wounds, spas, dishes, and surfaces. They kill bacteria and other potentially harmful microorganisms through a process known as sterilization. Their reactivity is also put to use in bleaching. Sodium hypochlorite, which is produced from chlorine, is the active ingredient of most fabric bleaches, and chlorine-derived bleaches are used in the production of some paper products. Chlorine also reacts with sodium to create sodium chloride, which is another name for table salt.

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In drug discovery, the incorporation of halogen atoms into a drug candidate results in analogues that are usually more lipophilic and less water-soluble.[21] As a consequence, halogen atoms are used to improve penetration through lipid membranes and tissues. It follows that there is a tendency for some halogenated drugs to accumulate in adipose tissue. The chemical reactivity of halogen atoms depends on both their point of attachment to the lead and the nature of the halogen. Aromatic halogen groups are far less reactive than aliphatic 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 are essential for humans. There are 0.5 milligrams per liter of fluorine in human blood. Human bones contain 0.2 to 1.2% fluorine. Human tissue contains

14 approximately 50 parts per billion of fluorine. A typical 70-kilogram human contains 3 to 6 grams of fluorine.[1] Chloride anions are essential to a large number of species, humans included. The concentration of chlorine in the dry weight of cereals is 10 to 20 parts per million, while in potatoes 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 contains 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.[1] 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.[1] Humans typically consume less than 100 micrograms of iodine per day. Iodine deficiency can cause mental retardation. Organoiodine compounds occur in humans in some of the glands, especially the thyroid gland, as well

15 as the stomach, epidermis, and immune system. Foods containing iodine include cod, oysters, shrimp, herring, lobsters, sunflower seeds, seaweed, and mushrooms. 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.[1] Astatine has no biological role.[1] Toxicity The halogens tend to decrease in toxicity towards the heavier halogens.[22] Fluorine gas is extremely toxic; breathing fluorine gas at a concentration of 0.1% for several minutes is 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 dental fluorosis, an aesthetic condition of the teeth.[23] 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

16 recommended levels in water fluoridation, a way to prevent dental caries, range from 0.7-1.2 mg/L to avoid the detrimental effects of fluoride while at the same time reaping the benefits.[24] People with levels between normal levels and those required for skeletal fluorosis tend to have symptoms similar to arthritis.[1] 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. Breathing in chlorine gas is highly painful.[22] Hydrochloric acid is a dangerous chemical.[1] Pure bromine is somewhat toxic, but less toxic than fluorine and chlorine. One hundred milligrams of bromine are lethal.[1] Bromide anions are also toxic, but less so that bromine. Bromide has a lethal does of 30 grams.[1] 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.[1] Astatine is very radioactive and thus highly dangerous.[1]

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