1911 Encyclopædia Britannica/Bromley
BROMINE (symbol Br, atomic weight 79.96), a chemical element of the halogen group, which takes its name from its pungent unpleasant smell (βρῶμος, a stench). It was first isolated by A.J. Balard in 1826 from the salts in the waters of the Mediterranean. He established its elementary character, and his researches were amplified by K.J. Löwig (1803-1890) in Das Brom und seine chemischen Verhaltnisse (1829). Bromine does not occur in nature in the uncombined condition, but in combination with various metals is very widely but sparingly distributed. Potassium, sodium and magnesium bromides are found in mineral waters, in river and sea-water, and occasionally in marine plants and animals. Its chief commercial sources are the salt deposits at Stassfurt in Prussian Saxony, in which magnesium bromide is found associated with various chlorides, and the brines of Michigan, Ohio, Pennsylvania and West Virginia, U.S.A.; small quantities are obtained from the mother liquors of Chile saltpetre and kelp. In combination with silver it is found as the mineral bromargyrite (bromite).
Manufacture.—The chief centres of the bromine industry are Stassfurt and the central district of Michigan. It is manufactured from the magnesium bromide contained in "bittern" (the mother liquor of the salt industry), by two processes, the continuous and the periodic. The continuous process depends upon the decomposition of the bromide by chlorine, which is generated in special stills. A regular current of chlorine mixed with steam is led in at the bottom of a tall tower filled with broken bricks, and there meets a descending stream of hot bittern: bromine is liberated and is swept out of the tower together with some chlorine, by the current of steam, and then condensed in a worm. Any uncondensed bromine vapour is absorbed by moist iron borings, and the resulting iron bromide is used for the manufacture of potassium bromide. The periodic process depends on the interaction between manganese dioxide (pyrolusite), sulphuric acid, and a bromide, and the operation is carried out in sandstone stills heated to 60° C., the product being condensed as in the continuous process. The substitution of potassium chlorate for pyrolusite is recommended when calcium chloride is present in the bittern. The crude bromine is purified by repeated shaking with potassium, sodium or ferrous bromide and subsequent redistillation. Commercial bromine is rarely pure, the chief impurities present in it being chlorine, hydrobromic acid, and bromoform (M. Hermann, Annalen, 1855, 95, p. 211). E. Gessner (Berichte, 1876, 9, p. 1507) removes chlorine by repeated shaking with water, followed by distillation over sulphuric acid; hydrobromic acid is removed by distillation with pure manganese dioxide, or mercuric oxide, and the product dried over sulphuric acid. J.S. Stas, in his stoichiometric researches, prepared chemically pure bromine from potassium bromide, by converting it into the bromate which was purified by repeated crystallization. By heating the bromate it was partially converted into the bromide, and the resulting mixture was distilled with sulphuric acid. The distillate was further purified by digestion with milk of lime, precipitation with water, and further digestion with calcium bromide and barium oxide, and was finally redistilled.
Characters.—Bromine at ordinary temperatures is a mobile liquid of fine red colour, which appears almost black in thick layers. It boils at 59° C. According to Sir W. Ramsay and S. Young, bromine, when dried over sulphuric acid, boils at 57.65° C., and when dried over phosphorus pentoxide, boils at 58.85° C. (under a pressure of 755.8 mm.), forming a deep red vapour, which exerts an irritating and directly poisonous action on the respiratory organs. It solidifies at -21° C. (Quincke) to a dark brown solid. Its specific gravity is 3.18828 (0/4°), latent heat of fusion 16.185 calories, latent heat of vaporization 45.6 calories, specific heat 0.1071. The specific heat of bromine vapour, at constant pressure, is 0.05504 and at constant volume is 0.04251 (K. Strecker). Bromine is soluble in water, to the extent of 3.226 grammes of bromine per 100 grammes of solution at 15° C., the solubility being slightly increased by the presence of potassium bromide. The solution is of an orange-red colour, and is quite permanent in the dark, but on exposure to light, gradually becomes colourless, owing to decomposition into hydrobromic acid and oxygen. By cooling the aqueous solution, hyacinth-red octahedra of a crystalline hydrate of composition Br·4H2O or Br2·8H2O are obtained (Bakhuis Roozeboom, Zeits. phys. Chem., 1888, 2. p. 449). Bromine is readily soluble in chloroform, alcohol and ether.
Its chemical properties are in general intermediate between those of chlorine and iodine; thus it requires the presence of a catalytic agent, or a fairly high temperature, to bring about its union with hydrogen. It does not combine directly with oxygen, nitrogen or carbon. With the other elements it unites to form bromides, often with explosive violence; phosphorus detonates in liquid bromine and inflames in the vapour; iron is occasionally used to absorb bromine vapour, potassium reacts energetically, but sodium requires to be heated to 200° C. The chief use of bromine in analytical chemistry is based upon the oxidizing action of bromine water. Bromine and bromine water both bleach organic colouring matters. The use of bromine in the extraction of gold (q.v.) was proposed by R. Wagner (Dingler's Journal, 218, p. 253) and others, but its cost has restricted its general application. Bromine is used extensively in organic chemistry as a substituting and oxidizing agent and also for the preparation of addition compounds. Reactions in which it is used in the liquid form, in vapour, in solution, and in the presence of the so-called "bromine carriers," have been studied. Sunlight affects the action of bromine vapour on organic compounds in various ways, sometimes retarding or accelerating the reaction, while in some cases the products are different (J. Schramm, Monatshefte fur Chemie, 1887, 8, p. 101). Some reactions, which are only possible by the aid of nascent bromine, are carried out by using solutions of sodium bromide and bromate, with the amount of sulphuric acid calculated according to the equation 5NaBr + NaBrO3 + 6H2SO4 = 6NaHSO4 + 3H2O + 6Br. (German Patent, 26642.) The diluents in which bromine is employed are usually ether, chloroform, acetic acid, hydrochloric acid, carbon bisulphide and water, and, less commonly, alcohol, potassium bromide and hydrobromic acid; the excess of bromine being removed by heating, by sulphurous acid or by shaking with mercury. The choice of solvent is important, for the velocity of the reaction and the nature of the product may vary according to the solvent used, thus A. Baeyer and F. Blom found that on brominating orthoacetamido-acetophenone in presence of water or acetic acid, the bromine goes into the benzene nucleus, whilst in chloroform or sulphuric acid or by use of bromine vapour it goes into the side chain as well. The action of bromine is sometimes accelerated by the use of compounds which behave catalytically, the more important of these substances being iodine, iron, ferric chloride, ferric bromide, aluminium bromide and phosphorus. For oxidizing purposes bromine is generally employed in aqueous and in alkaline solutions, one of its most important applications being by Emil Fischer (Berichte, 1889, 22, p. 362) in his researches on the sugars. The atomic weight of bromine has been determined by J.S. Stas and C. Marignac from the analysis of potassium bromide, and of silver bromide. G.P. Baxter (Zeit. anorg. Chem. 1906, 50, p. 389) determined the ratios Ag: AgBr, and AgCl: Ag Br.
Hydrobromic Acid.—This acid, HBr, the only compound of hydrogen and bromine, is in many respects similar to hydrochloric acid, but is rather less stable. It may be prepared by passing hydrogen gas and bromine vapour through a tube containing a heated platinum spiral. It cannot be prepared with any degree of purity by the action of concentrated sulphuric acid on bromides, since secondary reactions take place, leading to the liberation of free bromine and formation of sulphur dioxide. The usual method employed for the preparation of the gas consists in dropping bromine on to a mixture of amorphous phosphorus and water, when a violent reaction takes place and the gas is rapidly liberated. It can be obtained also, although in a somewhat impure condition, by the direct action of bromine on various saturated hydrocarbons (e.g. paraffin-wax), while an aqueous solution may be obtained by passing sulphuretted hydrogen through bromine water. Alexander Scott (Journal of Chem. Soc., 1900, 77, p. 648) prepares pure hydrobromic acid by covering bromine, which is contained in a large flask, with a layer of water, and passing sulphur dioxide into the water above the surface of the bromine, until the whole is of a pale yellow colour; the resulting solution is then distilled in a slow current of air and finally purified by distillation over barium bromide. At ordinary temperatures hydrobromic acid is a colourless gas which fumes strongly in moist air, and has an acid taste and reaction. It can be condensed to a liquid, which boils at -64.9° C. (under a pressure of 738.2 mm.), and, by still further cooling, gives colourless crystals which melt at -88.5° C. It is readily soluble in water, forming the aqueous acid, which when saturated at 0° C. has a specific gravity of 1.78. When boiled, the aqueous acid loses either acid or water until a solution of constant boiling point is obtained, containing 48% of the acid and boiling at 126° C. under atmospheric pressure; should the pressure, however, vary, the strength of the solution boiling at a constant temperature varies also. Hydrobromic acid is one of the "strong" acids, being ionized to a very large extent even in concentrated solution, as shown by the molecular conductivity increasing by only a small amount over a wide range of dilution.
Bromides.—Hydrobromic acid reacts with metallic oxides, hydroxides and carbonates to form bromides, which can in many cases be obtained also by the direct union of the metals with bromine. As a class, the metallic bromides are solids at ordinary temperatures, which fuse readily and volatilize on heating. The majority are soluble in water, the chief exceptions being silver bromide, mercurous bromide, palladious bromide and lead bromide; the last is, however, soluble in hot water. They are decomposed by chlorine, with liberation of bromine and formation of metallic chlorides; concentrated sulphuric acid also decomposes them, with formation of a metallic sulphate and liberation of bromine and sulphur dioxide. The non-metallic bromides are usually liquids, which are readily decomposed by water. Hydrobromic acid and its salts can be readily detected by the addition of chlorine water to their aqueous solutions, when bromine is liberated; or by warming with concentrated sulphuric acid and manganese dioxide, the same result being obtained. Silver nitrate in the presence of nitric acid gives with bromides a pale yellow precipitate of silver bromide, AgBr, which is sparingly soluble in ammonia. For their quantitative determination they are precipitated in nitric acid solution by means of silver nitrate, and the silver bromide well washed, dried and weighed.
No oxides of bromine have as yet been isolated, but three oxy-acids are known, namely hypobromous acid, HBrO, bromous acid, HBrO2, and bromic acid, HBrO3. Hypobromous acid is obtained by shaking together bromine water and precipitated mercuric oxide, followed by distillation of the dilute solution in vacuo at low temperature (about 40° C.). It is a very unstable compound, breaking up, on heating, into bromine and oxygen. The aqueous solution is light yellow in colour, and possesses strong bleaching properties. Bromous acid is formed by adding bromine to a saturated solution of silver nitrate (A. H. Richards, J. Soc Chem. Ind., 1906, 25, p. 4). Bromic acid is obtained by the addition of the calculated amount of sulphuric acid (previously diluted with water) to the barium salt; by the action of bromine on the silver salt, in the presence of water, 5AgBrO3 + 3Br2 + 3H2O = 5AgBr + 6HBrO3, or by passing chlorine through a solution of bromine in water. The acid is only known in the form of its aqueous solution; this is, however, very unstable, decomposing on being heated to 100° C. into water, oxygen and bromine. By reducing agents such, for example, as sulphuretted hydrogen and sulphur-dioxide, it is rapidly converted into hydrobromic acid. Hydrobromic acid decomposes it according to the equation HBrO3 + 5HBr = 3H2O + 3Br2. Its salts are known as bromates, and are as a general rule difficultly soluble in water, and decomposed by heat, with evolution of oxygen.
Applications.—The salts of bromine are widely used in photography, especially bromide of silver. For antiseptic purposes it has been prepared as "bromum solidificatum," which consists of kieselguhr or similar substance impregnated with about 75% of its weight of bromine. In medicine it is largely employed in the form of bromides of potassium, sodium and ammonium, as well as in combination with alkaloids and other substances.
Medicinal Use.—Bromide of potassium is the safest and most generally applicable sedative of the nervous system. Whilst very weak, its action is perfectly balanced throughout all nervous tissue, so much so that Sir Thomas Lauder Brunton has suggested its action to be due to its replacement of sodium chloride (common salt) in the fluids of the nervous system. Hence bromide of potassium—or bromide of sodium, which is possibly somewhat safer still though not quite so certain in its action—is used as a hypnotic, as the standard anaphrodisiac, as a sedative in mania and all forms of morbid mental excitement, and in hyperaesthesia of all kinds. Its most striking success is in epilepsy, for which it is the specific remedy. It may be given in doses of from ten to fifty grains or more, and may be continued without ill effect for long periods in grave cases of epilepsy (grand mal). Of the three bromides in common use the potassium salt is the most rapid and certain in its action, but may depress the heart in morbid states of that organ; in such cases the sodium salt—of which the base is inert—may be employed. In whooping-cough, when a sedative is required but a stimulant is also indicated, ammonium bromide is often invaluable. The conditions in which bromides are most frequently used are insomnia, epilepsy, whooping-cough, delirium tremens, asthma, migraine, laryngismus stridulus, the symptoms often attendant upon the climacteric in women, hysteria, neuralgia, certain nervous disorders of the heart, strychnine poisoning, nymphomania and spermatorrhoea. Hydrobromic acid is often used to relieve or prevent the headache and singing in the ears that may follow the administration of quinine and of salicylic acid or salicylates.