Бром: қасиеттері, тарихы және қолданылуы

Bromine is a chemical element; it has symbol Br and atomic number 35. It is a volatile red brown liquid at room temperature that evaporates readily to form a similarly coloured vapour. Its properties are intermediate between those of chlorine and iodine. Isolated independently by two chemists, Carl Jacob Löwig (in 1825) and Antoine Jérôme Balard (in 1826), its name was derived from the Ancient Greek βρῶμος (bromos) meaning "stench", referring to its sharp and pungent smell. Elemental bromine is very reactive and thus does not occur as a free element in nature. Instead, it can be isolated from colourless soluble crystalline mineral halide salts analogous to table salt, a property it shares with the other halogens. While it is rather rare in the Earth's crust, the high solubility of the bromide ion (Br) has caused its accumulation in the oceans. Commercially the element is easily extracted from brine evaporation ponds, mostly in the United States and Israel. The mass of bromine in the oceans is about one three hundredth that of chlorine. At standard conditions for temperature and pressure it is a liquid; the only other element that is liquid under these conditions is mercury. At high temperatures, organobromine compounds readily dissociate to yield free bromine atoms, a process that stops free radical chemical chain reactions. This effect makes organobromine compounds useful as fire retardants, and more than half the bromine produced worldwide each year is put to this purpose. The same property causes ultraviolet sunlight to dissociate volatile organobromine compounds in the atmosphere to yield free bromine atoms, causing ozone depletion. As a result, many organobromine compounds—such as the pesticide methyl bromide—are no longer used. Bromine compounds are still used in well drilling fluids, in photographic film, and as an intermediate in the manufacture of organic chemicals. Large amounts of bromide salts are toxic from the action of soluble bromide ions, causing bromism. However, bromine is beneficial for human eosinophils,

Löwig isolated bromine from a mineral water spring from his hometown Bad Kreuznach in 1825. Löwig used a solution of the mineral salt saturated with chlorine and extracted the bromine with diethyl ether. After evaporation of the ether, a brown liquid remained. With this liquid as a sample of his work he applied for a position in the laboratory of Leopold Gmelin in Heidelberg. The publication of the results was delayed and Balard published his results first. After the French chemists Louis Nicolas Vauquelin, Louis Jacques Thénard, and Joseph Louis Gay Lussac approved the experiments of the young pharmacist Balard, the results were presented at a lecture of the Académie des Sciences and published in Annales de Chimie et Physique. Other sources claim that the French chemist and physicist Joseph Louis Gay Lussac suggested the name brôme for the characteristic smell of the vapors. Apart from some minor medical applications, the first commercial use was the daguerreotype. In 1840, bromine was discovered to have some advantages over the previously used iodine vapor to create the light sensitive silver halide layer in daguerreotypy. By 1864, a 25% solution of liquid bromine in .75 molar aqueous potassium bromide
was widely used
to treat gangrene during the American Civil War, before the publications of Joseph Lister and Pasteur. Potassium bromide and sodium bromide were used as anticonvulsants and sedatives in the late 19th and early 20th centuries, but were gradually superseded by chloral hydrate and then by the barbiturates. In the early years of the First World War, bromine compounds such as xylyl bromide were used as poison gas.

Bromine is the third halogen, being a nonmetal in group 17 of the periodic table. Its properties are thus similar to those of fluorine, chlorine, and iodine, and tend to be intermediate between those of the two neighbouring halogens, chlorine, and iodine. Bromine has the electron configuration [Ar]4s3d4p, with the seven electrons in the fourth and outermost shell acting as its valence electrons. Like all halogens, it is thus one electron short of a full octet, and is hence a strong oxidising agent, reacting with many elements in order to complete its outer shell. Corresponding to periodic trends, it is intermediate in electronegativity between chlorine and iodine (F: 3.98, Cl: 3.16, Br: 2.96, I: 2.66), and is less reactive than chlorine and more reactive than iodine. It is also a weaker oxidising agent than chlorine, but a stronger one than iodine. Conversely, the bromide ion is a weaker reducing agent than iodide, but a stronger one than chloride. It is intermediate in atomic radius between chlorine and iodine, and this leads to many of its atomic properties being similarly intermediate in value between chlorine and iodine, such as first ionisation energy, electron affinity, enthalpy of dissociation of the X molecule (X = Cl, Br, I), ionic radius, and X–X bond length. All four stable halogens experience intermolecular van der Waals forces of attraction, and their strength increases together with the number of electrons among all homonuclear diatomic halogen molecules. Thus, the melting and boiling points of bromine are intermediate between those of chlorine and iodine. As a result of the increasing molecular weight of the halogens down the group, the density and heats of fusion and vaporisation of bromine are again intermediate between those of chlorine and iodine, although all their heats of vaporisation are fairly low (leading to high volatility) thanks to their diatomic molecular structure. The colour fades at low temperatures so that solid bromine at −195 °C is pale yellow.

Bromine has two stable isotopes, Br and Br. These are its only two natural isotopes, with Br making up 51% of natural bromine and Br making up the remaining 49%. Both have nuclear spin 3/2− and thus may be used for nuclear magnetic resonance, although Br is more favourable. The relatively 1:1 distribution of the two isotopes in nature is helpful in identification of bromine containing compounds using mass spectroscopy. Other bromine isotopes are all radioactive, with half lives too short to occur in nature. Of these, the most important are Br (t = 17.7 min), Br (t = 4.421 h), and Br (t = 35.28 h), which may be produced from the neutron activation of natural bromine.

Like the other carbon–halogen bonds, the C–Br bond is a common functional group that forms part of core organic chemistry. Formally, compounds with this functional group may be considered organic derivatives of the bromide anion. Due to the difference of electronegativity between bromine (2.96) and carbon (2.55), the carbon atom in a C–Br bond is electron deficient and thus electrophilic. The reactivity of organobromine compounds resembles but is intermediate between the reactivity of organochlorine and organoiodine compounds. For many applications, organobromides represent a compromise of reactivity and cost. Organobromides are the most common organohalides in nature, even though the concentration of bromide is only 0.3% of that for chloride in sea water, because of the easy oxidation of bromide to the equivalent of Br, a potent electrophile. The enzyme bromoperoxidase catalyzes this reaction. The oceans are estimated to release 1–2 million tons of bromoform and 56,000 tons of bromomethane annually.

Bromine is significantly less abundant in the crust than fluorine or chlorine, comprising only 2.5 parts per million of the Earth's crustal rocks, and then only as bromide salts. It is the forty sixth most abundant element in Earth's crust. It is significantly more abundant in the oceans, resulting from long term leaching. There, it makes up 65 parts per million, corresponding to a ratio of about one bromine atom for every 660 chlorine atoms. Salt lakes and brine wells may have higher bromine concentrations: for example, the Dead Sea contains 0.4% bromide ions. It is from these sources that bromine extraction is mostly economically feasible. The main sources of bromine production are Israel and Jordan. The element is liberated by halogen exchange, using chlorine gas to oxidise Br to Br. This is then removed with a blast of steam or air, and is then condensed and purified. Today, bromine is transported in large capacity metal drums or lead lined tanks that can hold hundreds of kilograms or even tonnes of bromine. The bromine industry is about one hundredth the size of the chlorine industry. Laboratory production is unnecessary because bromine is commercially available and has a long shelf life.

A wide variety of organobromine compounds are used in industry. Some are prepared from bromine and others are prepared from hydrogen bromide, which is obtained by burning hydrogen in bromine.

Brominated flame retardants represent a commodity of growing importance, and make up the largest commercial use of bromine. When the brominated material burns, the flame retardant produces hydrobromic acid which interferes in the radical chain reaction of the oxidation reaction of the fire. The mechanism is that the highly reactive hydrogen radicals, oxygen radicals, and hydroxyl radicals react with hydrobromic acid to form less reactive bromine radicals (i. e., free bromine atoms). Bromine atoms may also react directly with other radicals to help terminate the free radical chain reactions that characterise combustion. To make brominated polymers and plastics, bromine containing compounds can be incorporated into the polymer during polymerisation. One method is to include a relatively small amount of brominated monomer during the polymerisation process. For example, vinyl bromide can be used in the production of polyethylene, polyvinyl chloride or polypropylene. Specific highly brominated molecules can also be added that participate in the polymerisation process. For example, tetrabromobisphenol A can be added to polyesters or epoxy resins, where it becomes part of the polymer. Epoxies used in printed circuit boards are normally made from such flame retardant resins, indicated by the FR in the abbreviation of the products (FR 4 and FR 2). In some cases, the bromine containing compound may be added after polymerisation. For example, decabromodiphenyl ether can be added to the final polymers. A number of gaseous or highly volatile brominated halomethane compounds are non toxic and make superior fire suppressant agents by this same mechanism, and are particularly effective in enclosed spaces such as submarines, airplanes, and spacecraft. However, they are expensive and their production and use has been greatly curtailed due to their effect as ozone depleting agents. They are no longer used in routine fire extinguishers, but retain niche uses in aerospace and military automatic fire suppression applications. They include bromochloromethane (Halon 1011, CHBrCl), bromochlorodifluoromethane (Halon 1211, CBrClF), and bromotrifluoromethane (Halon 1301, CBrF).

Silver bromide is used, either alone or in combination with silver chloride and silver iodide, as the light sensitive constituent of photographic emulsions. Brominated vegetable oil (BVO), a complex mixture of plant derived triglycerides that have been reacted to contain atoms of the element bromine bonded to the molecules, is used primarily to help emulsify citrus flavored soft drinks, preventing them from separating during distribution. Poisonous bromomethane was widely used as pesticide to fumigate soil and to fumigate housing, by the tenting method. Ethylene bromide was similarly used. In pharmacology, inorganic bromide compounds, especially potassium bromide, were frequently used as general sedatives in the 19th and early 20th century. Bromides in the form of simple salts are still used as anticonvulsants in both veterinary and human medicine, although the latter use varies from country to country. For example, the U. S. Food and Drug Administration (FDA) does not approve bromide for the treatment of any disease, and sodium bromide was removed from over the counter sedative products like Bromo Seltzer, in 1975. Commercially available organobromine pharmaceuticals include the vasodilator nicergoline, the sedative brotizolam, the anticancer agent pipobroman, and the antiseptic merbromin. Otherwise, organobromine compounds are rarely pharmaceutically useful, in contrast to the situation for organofluorine compounds. Several drugs are produced as the bromide (or equivalents, hydrobromide) salts, but in such cases bromide serves as an innocuous counterion of no biological significance. Because it has similar antiseptic qualities to chlorine, bromine can be used in the same manner as chlorine as a disinfectant or antimicrobial in applications such as swimming pools. However, bromine is usually not used outside for these applications due to it being relatively more expensive than chlorine and the absence of a stabilizer to protect it from the sun. For indoor pools, it can be a good option as it is effective at a wider pH range. It is also more stable in a heated pool or hot tub.

A 2014 study suggests that bromine (in the form of bromide ion) is a necessary cofactor in the biosynthesis of collagen IV, making the element essential to basement membrane architecture and tissue development in animals. Nevertheless, no clear deprivation symptoms or syndromes have been documented in mammals. In other biological functions, bromine may be non essential but still beneficial when it takes the place of chlorine. For example, in the presence of hydrogen peroxide, HO, formed by the eosinophil, and either chloride, iodide, thiocyanate, or bromide ions, eosinophil peroxidase provides a potent mechanism by which eosinophils kill multicellular parasites (such as the nematode worms involved in filariasis) and some bacteria (such as tuberculosis bacteria). Eosinophil peroxidase is a haloperoxidase that preferentially uses bromide over chloride for this purpose, generating hypobromite (hypobromous acid), although the use of chloride is possible. α Haloesters are generally thought of as highly reactive and consequently toxic intermediates in organic synthesis. Nevertheless, mammals, including humans, cats, and rats, appear to biosynthesize traces of an α bromoester, 2 octyl 4 bromo 3 oxobutanoate, which is found in their cerebrospinal fluid and appears to play a yet unclarified role in inducing REM sleep. Marine organisms are the main source of organobromine compounds, and it is in these organisms that bromine is more firmly shown to be essential. More than 1600 such organobromine compounds were identified by 1999. The most abundant is methyl bromide (CHBr), of which an estimated 56,000 tonnes is produced by marine algae each year. The essential oil of the Hawaiian alga Asparagopsis taxiformis consists of 80% bromoform. Most of such organobromine compounds in the sea are made by the action of a unique algal enzyme, vanadium bromoperoxidase. The bromide anion is not very toxic: a normal daily intake is 2 to 8 milligrams. Bromism is caused by a neurotoxic effect on the brain which results in somnolence, psychosis, seizures and delirium. Elemental bromine (Br) is toxic and causes chemical burns on human flesh. Inhaling bromine gas results in similar irritation of the respiratory tract, causing coughing, choking, shortness of breath, and death if inhaled in large enough amounts. Chronic exposure may lead to frequent bronchial infections and a general deterioration of health. As a strong oxidising agent, bromine is incompatible with most organic and inorganic compounds. Caution is required when transporting bromine; it is commonly carried in steel tanks lined with lead, supported by strong metal frames. Bromine is classified as an extremely hazardous substance in the United States as defined in Section 302 of the U. S. Emergency Planning and Community Right to Know Act (42 U. S. C. 11002), and is subject to strict reporting requirements by facilities which produce, store, or use it in significant quantities.