1911 Encyclopædia Britannica/Gallium

GALLIUM (symbol Ga; atomic weight 69·9), one of the metallic chemical elements. It was discovered in 1875 through its spectrum, in a specimen of zinc blende by Lecoq de Boisbaudran (Comptes rendus, 1875, 81, p. 493, and following years). The chief chemical and physical properties of gallium had been predicted many years before by D. Mendeléeff (c. 1869) from a consideration of the properties of aluminium, indium and zinc (see Element). The metal is obtained from zinc blende (which only contains it in very small quantity) by dissolving the mineral in an acid, and precipitating the gallium by metallic zinc. The precipitate is dissolved in hydrochloric acid and foreign metals are removed by sulphuretted hydrogen; the residual liquid being then fractionally precipitated by sodium carbonate, which throws out the gallium before the zinc. This precipitate is converted into gallium sulphate and finally into a pure specimen of the oxide, from which the metal is obtained by the electrolysis of an alkaline solution. Gallium crystallizes in greyish-white octahedra which melt at 30·15° C. to a silvery-white liquid. It is very hard and but slightly malleable and flexible, although in thin plates it may be bent several times without breaking. The specific gravity of the solid form is 5·956 (24·5° C.), of the liquid 6·069, whilst the specific heats of the two varieties are, for the solid form 0·079 (12-23° C.) and for the liquid 0·082 (106-119°) [M. Berthelot, Comptes rendus, 1878, 86, p. 786]. It is not appreciably volatilized at a red heat. Chlorine acts on it readily in the cold, bromine not so easily, and iodine only when the mixture is heated. The atomic weight of gallium has been determined by Lecoq de Boisbaudran by ignition of gallium ammonium alum, and also by L. Meyer and K. Seubert.

Gallium oxide Ga₂O₃ is obtained when the nitrate is heated, or by solution of the metal in nitric acid and ignition of the nitrate. It forms a white friable mass which after ignition is insoluble in acids. On heating to redness in a stream of hydrogen it forms a bluish mass which is probably a lower oxide of composition GaO. Gallium forms colourless salts, which in neutral dilute aqueous solutions are converted on heating into basic salts. The gallium salts are precipitated by alkaline carbonates and by barium carbonate, but not by sulphuretted hydrogen unless in acetic acid solution. Potassium ferrocyanide gives a precipitate even in very dilute solution. In neutral solutions, zinc gives a precipitate of gallium oxide. By heating gallium in a regulated stream of chlorine the dichloride GaCl₂ is obtained as a crystalline mass, which melts at 164° C. and readily decomposes on exposure to moist air. The trichloride GaCl₃ is similarly formed when the metal is heated in a rapid stream of chlorine, and may be purified by distillation in an atmosphere of nitrogen. It forms very deliquescent long white needles melting at 75·5° C. and boiling at 215-220° C. The bromide, iodide and sulphate are known, as is also gallium ammonium alum. Gallium is best detected by means of its spark spectrum, which gives two violet lines of wave length 4171 and 4031.