the name schistos, and the mode of formation, there can be little doubt that this species was the salt which forms spontaneously on certain slaty minerals, as alum slate and bituminous shale, and which consists chiefly of the sulphates of iron and aluminium. Possibly in certain places the iron sulphate may have been nearly wanting, and then the salt would be white, and would answer, as Pliny says it did, for dyeing bright colours. Several other species of alumen are described by Pliny, but we are unable to make out to what minerals he alludes.
The alumen of the ancients, then, was not the same with the alum of the moderns. It was most commonly an iron sulphate, sometimes probably an aluminium sulphate, and usually a mixture of the two. But the ancients were unacquainted with our alum. They were acquainted with a crystallized iron sulphate, and distinguished it by the names of misy, sory, chalcanthum (Pliny xxxiv. 12). As alum and green vitriol were applied to a variety of substances in common, and as both are distinguished by a sweetish and astringent taste, writers, even after the discovery of alum, do not seem to have discriminated the two salts accurately from each other. In the writings of the alchemists we find the words misy, sory, chalcanthum applied to alum as well as to iron sulphate; and the name atramentum sutorium, which ought to belong, one would suppose, exclusively to green vitriol, applied indifferently to both. Various minerals are employed in the manufacture of alum, the most important being alunite (q.v.) or alum-stone, alum schist, bauxite and cryolite.
In order to obtain alum from alunite, it is calcined and then exposed to the action of air for a considerable time. During this exposure it is kept continually moistened with water, so that it ultimately falls to a very fine powder. This powder is then lixiviated with hot water, the liquor decanted, and the alum allowed to crystallize. The alum schists employed in the manufacture of alum are mixtures of iron pyrites, aluminium silicate and various bituminous substances, and are found in upper Bavaria, Bohemia, Belgium and Scotland. These are either roasted or exposed to the weathering action of the air. In the roasting process, sulphuric acid is formed and acts on the clay to form aluminium sulphate, a similar condition of affairs being produced during weathering. The mass is now systematically extracted with water, and a solution of aluminium sulphate of specific gravity 1·16 is prepared. This solution is allowed to stand for some time (in order that any calcium sulphate and basic ferric sulphate may separate), and is then evaporated until ferrous sulphate crystallizes on cooling; it is then drawn off and evaporated until it attains a specific gravity of 1·40. It is now allowed to stand for some time, decanted from any sediment, and finally mixed with the calculated quantity of potassium sulphate (or if ammonium alum is required, with ammonium sulphate), well agitated, and the alum is thrown down as a finely-divided precipitate of alum meal. If much iron should be present in the shale then it is preferable to use potassium chloride in place of potassium sulphate.
In the preparation of alum from clays or from bauxite, the material is gently calcined, then mixed with sulphuric acid and heated gradually to boiling; it is allowed to stand for some time, the clear solution drawn off and mixed with acid potassium sulphate and allowed to crystallize. When cryolite is used for the preparation of alum, it is mixed with calcium carbonate and heated. By this means, sodium aluminate is formed; it is then extracted with water and precipitated either by sodium bicarbonate or by passing a current of carbon dioxide through the solution. The precipitate is then dissolved in sulphuric acid, the requisite amount of potassium sulphate added and the solution allowed to crystallize.
Potash alum, K2SO4·Al2(SO4)3·24H2O, crystallizes in regular octahedra and is very soluble in water. The solution reddens litmus and is an astringent. When heated to nearly a red heat it gives a porous friable mass which is known as “burnt alum.” It fuses at 92° C. in its own water of crystallization. “Neutral alum” is obtained by the addition of as much sodium carbonate to a solution of alum as will begin to cause the separation of alumina; it is much used in mordanting. Alum finds application as a mordant, in the preparation of lakes for sizing hand-made paper and in the clarifying of turbid liquids.
Sodium alum, Na2SO4·Al2(SO4)3·24H2O, occurs in nature as the mineral mendozite. It is very soluble in water, and is extremely difficult to purify. In the preparation of this salt, it is preferable to mix the component solutions in the cold, and to evaporate them at a temperature not exceeding 60° C. 100 parts of water dissolve 110 parts of sodium alum at 0° C. (W. A. Tilden, Jour. Chem. Soc., 1884, 45, p. 409), and 51 parts at 16° C. (E. Augé, Comptes rendus, 1890, 110, p. 1139).
Chrome alum, K2SO4·Cr2(SO4)3·24H2O, appears chiefly as a by-product in the manufacture of alizarin, and as a product of the reaction in bichromate batteries. The solubility of the various alums in water varies greatly, sodium alum being readily soluble in water, whilst caesium and rubidium alums are only sparingly soluble. The various solubilities are shown in the following table:—
| Ammonium Alum. | Caesium Alum. | Potash Alum. | Rubidium Alum. | ||||
| t°C. | 100 parts water dissolve. |
t°C. | 100 parts water dissolve. |
t°C. | 100 parts water dissolve. |
t°C. | 100 parts water dissolve. |
| 0 | 2·62 | 0 | 0·19 | 0 | 3·9 | 0 | 0·71 |
| 10 | 4·5 | 10 | 0·29 | 10 | 9·52 | 10 | 1·09 |
| 50 | 15·9 | 50 | 1·235 | 50 | 44·11 | 50 | 4·98 |
| 80 | 35·2 | 80 | 5·29 | 80 | 134·47 | 80 | 21·60 |
| 100 | 70·83 | 100 | 357·48 | ||||
| Poggiale Ann. Chlm. phys. [3] 8, p. 467 |
C. Setterberg Ann. 1882, 211, p. 104. |
Poggiale | C. Setterberg | ||||
ALUMINIUM (symbol Al; atomic weight 27·0), a metallic chemical element. Although never met with in the free state, aluminium is very widely distributed in combination, principally as silicates. The word is derived from the Lat. alumen (see Alum), and is probably akin to the Gr. ἄλς (the root of salt, halogen, &c.). In 1722 F. Hoffmann announced the base of alum to be an individual substance; L. B. Guyton de Morveau suggested that this base should be called alumine, after Sel alumineux, the French name for alum; and about 1820 the word was changed into alumina. In 1760 the French chemist, T. Baron de Henouville, unsuccessfully attempted “to reduce the base of alum” to a metal, and shortly afterwards various other investigators essayed the problem in vain. In 1808 Sir Humphry Davy, fresh from the electrolytic isolation of potassium and sodium, attempted to decompose alumina by heating it with potash in a platinum crucible and submitting the mixture to a current of electricity; in 1809, with a more powerful battery, he raised iron wire to a red heat in contact with alumina, and obtained distinct evidence of the production of an iron-aluminium alloy. Naming the new metal in anticipation of its actual birth, he called it alumium; but for the sake of analogy he was soon persuaded to change the word to aluminum, in which form, alternately with aluminium, it occurs in chemical literature for some thirty years.
In the year 1824, endeavouring to prepare it by chemical means, H. C. Oersted heated its chloride with potassium amalgam, and failed in his object simply by reason of the mercury, so that when F. Wöhler repeated the experiment at Göttingen in 1827, employing potassium alone as the Preparation.reducing agent, he obtained it in the metallic state for the first time. Contaminated as it was with potassium and with platinum from the crucible, the metal formed a grey powder and was far from pure; but in 1845 he improved his process and succeeded in producing metallic globules wherewith he examined its chief
