1911 Encyclopædia Britannica/Boron
BORON (symbol B, atomic weight 11), one of the non-metallic elements, occurring in nature in the form of boracic (boric) acid, and in various borates such as borax, tincal, boronatrocalcite and boracite. It was isolated by J. Gay Lussac and L. Thénard in 1808 by heating boron trioxide with potassium, in an iron tube. It was also isolated at about the same time by Sir H. Davy, from boracic acid. It may be obtained as a dark brown amorphous powder by placing a mixture of 10 parts of the roughly powdered oxide with 6 parts of metallic sodium in a red-hot crucible, and covering the mixture with a layer of well-dried common salt. After the vigorous reaction has ceased and all the sodium has been used up, the mass is thrown into dilute hydrochloric acid, when the soluble sodium salts go into solution, and the insoluble boron remains as a brown powder, which may by filtered off and dried. H. Moissan (Ann. Chim. Phys., 1895, 6, p. 296) heats three parts of the oxide with one part of magnesium powder. The dark product obtained is washed with water, hydrochloric acid and hydrofluoric acid, and finally calcined again with the oxide or with borax, being protected from air during the operation by a layer of charcoal. Pure amorphous boron is a chestnut-coloured powder of specific gravity 2.45; it sublimes in the electric arc, is totally unaffected by air at ordinary temperatures, and burns on strong ignition with production of the oxide B2O3 and the nitride BN. It combines directly with fluorine at ordinary temperature, and with chlorine, bromine and sulphur on heating. It does not react with the alkali metals, but combines with magnesium at a low red heat to form a boride, and with other metals at more or less elevated temperatures. It reduces many metallic oxides, such as lead monoxide and cupric oxide, and decomposes water at a red heat. Heated with sulphuric acid and with nitric acid it is oxidized to boric acid, whilst on fusion with alkaline carbonates and hydroxides it gives a borate of the alkali metal. Like silicon and carbon, very varying values had been given for its specific heat, until H. F. Weber showed that the specific heat increases rapidly with increasing temperature. By strongly heating a mixture of boron trioxide and aluminium, protected from the air by a layer of charcoal, F. Wöhler and H. Sainte-Claire Deville obtained a grey product, from which, on dissolving out the aluminium with sodium hydroxide, they obtained a crystalline product, which they thought to be a modification of boron, but which was shown later to be a mixture of aluminium borides with more or less carbon. Boron dissolves in molten aluminium, and on cooling, transparent, almost colourless crystals are obtained, possessing a lustre, hardness and refractivity near that of the diamond. In 1904 K. A. Kühne (D.R.P. 147,871) described a process in which external heating is not necessary, a mixture of aluminium turnings, sulphur and boric acid being ignited by a hot iron rod, the resulting aluminium sulphide, formed as a by-product, being decomposed by water.
Boron hydride has probably never been isolated in the pure condition; on heating boron trioxide with magnesium filings, a magnesium boride Mg3B2 is obtained, and if this be decomposed with dilute hydrochloric acid a very evil-smelling gas, consisting of a mixture of hydrogen and boron hydride, is obtained. This mixture burns with a green flame forming boron trioxide; whilst boron is deposited on passing the gas mixture through a hot tube, or on depressing a cold surface in the gas flame. By cooling it with liquid air Sir W. Ramsay and H. S. Hatfield obtained from it a gas of composition B3H3. The mixture probably contained also some BH3 (W. Ramsay and H. S. Hatfield, Proc. Chem. Soc., 17, p. 152). Boron fluoride BF3 was first prepared in 1808 by Gay Lussac and L. Thénard and is best obtained by heating a mixture of the trioxide and fluorspar with concentrated sulphuric acid. It is a colourless pungent gas which is exceedingly soluble in water. It fumes strongly in air, and does not attack glass. It rapidly absorbs the elements of water wherever possible, so that a strip of paper plunged into the gas is rapidly charred. It does not burn, neither does it support combustion. A saturated solution of the gas, in water, is a colourless, oily, strongly fuming liquid which after a time decomposes, with separation of metaboric acid, leaving hydrofluoboric acid HF·BF3 in solution. This acid cannot be isolated in the free condition, but many of its salts are known. Boron fluoride also combines with ammonia gas, equal volumes of the two gases giving a white crystalline solid of composition BF3·NH3; with excess of ammonia gas, colourless liquids BF3·2NH3 and BF3·3NH3 are produced, which on heating lose ammonia and are converted into the solid form.
Boron chloride BCl3 results when amorphous boron is heated in chlorine gas, or more readily, on passing a stream of chlorine over a heated mixture of boron trioxide and charcoal, the volatile product being condensed in a tube surrounded by a freezing mixture. It is a colourless fuming liquid boiling at 17–18° C, and is readily decomposed by water with formation of boric and hydrochloric acids. It unites readily with ammonia gas forming a white crystalline solid of composition 2BCl3·3NH3.
Boron bromide BBr3 can be formed by direct union of the two elements, but is best obtained by the method used for the preparation of the chloride. It is a colourless fuming liquid boiling at 90.5° C. With water and with ammonia it undergoes the same reactions as the chloride. Boron and iodine do not combine directly, but gaseous hydriodic acid reacts with amorphous boron to form the iodide, BI3, which can also be obtained by passing boron chloride and hydriodic acid through a red-hot porcelain tube. It is a white crystalline solid of melting point 43 C.; it boils at 210° C., and it can be distilled without decomposition. It is decomposed by water, and with a solution of yellow phosphorus in carbon bisulphide it gives a red powder of composition PBI2, which sublimes in vacuo at 210° C. to red crystals, and when heated in a current of hydrogen loses its iodine and leaves a residue of boron phosphide PB.
Boron nitride BN is formed when boron is burned either in air or in nitrogen, but can be obtained more readily by heating to redness in a platinum crucible a mixture of one part of anhydrous borax with two parts of dry ammonium chloride. After fusion, the melt is well washed with dilute hydrochloric acid and then with water, the nitride remaining as a white powder. It can also be prepared by heating borimide B2(NH)3; or by heating boron trioxide with a metallic cyanide. It is insoluble in water and unaffected by most reagents, but when heated in a current of steam or boiled for some time with a caustic alkali, slowly decomposes with evolution of ammonia and the formation of boron trioxide or an alkaline borate; it dissolves slowly in hydrofluoric acid.
Borimide B2(NH)3 is obtained on long heating of the compound B2S3·6NH2 in a stream of hydrogen, or ammonia gas at 115–120° C. It is a white solid which decomposes on heating into boron nitride and ammonia. Long-continued heating with water also decomposes it slowly.
Boron sulphide B2S3 can be obtained by the direct union of the two elements at a white heat or from the tri-iodide and sulphur at 440° C., but is most conveniently prepared by heating a mixture of the trioxide and carbon in a stream of carbon bisulphide vapour. It forms slightly coloured small crystals possessing a strong disagreeable smell, and is rapidly decomposed by water with the formation of boric acid and sulphuretted hydrogen. A pentasulphide B2S5 is prepared, in an impure condition, by heating a solution of sulphur in carbon bisulphide with boron iodide, and forms a white crystalline powder which decomposes under the influence of water into sulphur, sulphuretted hydrogen and boric acid.
Boron trioxide B2O3 is the only known oxide of boron; and may be prepared by heating amorphous boron in oxygen, or better, by strongly igniting boric acid. After fusion the mass solidifies to a transparent vitreous solid which dissolves readily in water to form boric acid (q.v.); it is exceedingly hygroscopic and even on standing in moist air becomes opaque through absorption of water and formation of boric acid. Its specific gravity is 1.83 (J. Dumas). It is not volatile below a white heat, and consequently, if heated with salts of more volatile acids, it expels the acid forming oxide from such salts; for example, if potassium sulphate be heated with boron trioxide, sulphur trioxide is liberated and potassium borate formed. It also possesses the power of combining with most metallic oxides at high temperatures, forming borates, which in many cases show characteristic colours. Many organic compounds of boron are known; thus, from the action of the trichloride on ethyl alcohol or on methyl alcohol, ethyl borate B(OC2H5)3 and methyl borate B(OCH3)3 are obtained. These are colourless liquids boiling at 119° C. and 72° C. respectively, and both are readily decomposed by water. By the action of zinc methyl on ethyl borate, in the requisite proportions, boron trimethyl is obtained, thus:—
2B(OC2H5)2 + 6Zn(CH3)2 = 2B(CH3)3 + 6Zn
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CH3 |
| OC2H5 |
as a colourless spontaneously inflammable gas of unbearable smell. Boron triethyl B(C2H5)3 is obtained in the same manner, by using zinc ethyl. It is a colourless spontaneously inflammable liquid of boiling point 95° C. By the action of one molecule of ethyl borate on two molecules of zinc ethyl, the compound B(C2H5)2·OC2H5 diethylboron ethoxide is obtained as a colourless liquid boiling at 102° C. By the action of water it is converted into B(C2H5)2·OH, and this latter compound on exposure to air takes up oxygen slowly, forming the compound B·C2H5·OC2H5·OH, which, with water, gives B(C2H5)·(OH)2. From the condensation of two molecules of ethyl borate with one molecule of zinc ethyl the compound B2·C2H5·(OC2H5)5 is obtained as a colourless liquid of boiling point. 112° C. Boron triethyl and boron trimethyl both combine with ammonia.
The atomic weight of boron has been determined by estimating the water content of pure borax (J. Berzelius), also by conversion of anhydrous borax into sodium chloride (W. Ramsay and E. Aston) and from analysis of the bromide and chloride (Sainte-Claire Deville); the values obtained ranging from 10.73 to 11.04. Boron can be estimated by precipitation as potassium fluoborate, which is insoluble in a mixture of potassium acetate and alcohol. For this purpose only boric acid or its potassium salt must be present; and to ensure this, the borate can be distilled with sulphuric acid and methyl alcohol and the volatile ester absorbed in potash.