ALUM, in chemistry, a term given to the crystallized double sulphates of the typical formula M2SO4.M2111.(SO4)324H2O, Where M is the sign of an alkali metal (potassium, sodium, rubidium, caesium), silver or ammonium, and M111 denotes one of the trivalent metals, aluminium, chromium or ferric iron. These salts are employed in dyeing and various other industrial processes. They are soluble in water, have an astringent, acid, and sweetish taste, react acid to litmus, and crystallize in regular octahedra. When heated they liquefy; and if the heating be continued, the water of crystallization is driven off, the salt froths and swells, and at last an amorphous powder remains.
Potash alum is the common alum of commerce, although both soda alum and ammonium alum are manufactured. The presence of sulphuric acid in potash alum was known to the alchemists. J. H. Pott and A. S. Marggraf demonstrated that alumina was another constituent. Pott in his Lithogeognosia showed that the precipitate obtained when an alkali is poured into a solution of alum is quite different from lime and chalk, with which it had been confounded by G. E. Stahl. Marggraf showed that alumina is one of the constituents of alum, but that this earth possesses peculiar properties, and is one of the ingredients in common clay (Experiences faites sur la terre de l'alun, Marggraf's Opusc. ii. 111) . He also showed that crystals of alum cannot be obtained by dissolving alumina in sulphuric acid and evaporating the solutions, but when a solution of potash or ammonia is dropped into this liquid, it immediately deposits perfect crystals of alum (Sur la regeneration de l'alun, Marggraf's Opusc. ii. 86).
T. O. Bergman also observed that the addition of potash or ammonia made the solution of alumina in sulphuric acid crystallize, but that the same effect was not produced by the addition of soda or of lime (De confectione aluminus, Bergman's Opusc. i. 225), and that potassium sulphate is frequently found in alum.
After M. H. Klaproth had discovered the presence of potassium in leucite and lepidolite, it occurred to L. N. Vauquelin that it was probably an ingredient likewise in many other minerals. Knowing that alum cannot be obtained in crystals without the addition of potash, he began to suspect that this alkali constituted an essential ingredient in the salt, and in 1797 he published a dissertation demonstrating that alum is a double salt, composed of sulphuric acid, alumina and potash (Annales de chimie, xxii. 258). Soon after, J. A. Chaptal published the analysis of four different kinds of alum, namely, Roman alum, Levant alum, British alum and alum manufactured by himself. This analysis led to the same result as that of Vauquelin (Ann. de chim xxii. 280).
The word alumen, which we translate alum, occurs in Pliny's Natural History. In the 15th chapter of his 35th book he gives a detailed description of it. By comparing this with the account of stupteria given by Dioscorides in the 123rd chapter of his 5th book, it is obvious that the two are identical. Pliny informs us that alumen was found naturally in the earth. He calls it salsugoterrae. Different substances were distinguished by the name of "alumen"; but they were all characterized by a certain degree of astringency, and were all employed in dyeing and medicine, the light-coloured alumen being useful in brilliant dyes, the dark-coloured only in dyeing black or very dark colours. One species was a liquid, which was apt to be adulterated; but when pure it had the property of blackening when added to pomegranate juice. This property seems to characterize a solution of iron sulphate in water; a solution of ordinary (potash) alum would possess no such property. Pliny says that there is another kind of alum which the Greeks call schistos. It forms in white threads upon the surface of certain stones. From 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 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 redens 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 deg. 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 deg. C. 100 parts of water dissolve 110 parts of sodium alum at 0 deg. C. (W. A. Tilden, Jour. Chem. Soc., 1884, 45, p. 409), and 51 parts at 16 deg. C. (E. Auge, Comptes rendus, 1890, 110, p. 1139).
Chrome alum, K2SO4.Cr2(SO 4/0)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 deg. C. 100 parts t deg. C. 100 parts t deg. C. 100 parts t deg. C. 100 parts
water water water water
dissolve dissolve dissolve 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 C. Setterberg Poggiale C. Setterberg
Ann. Chim. phys. Ann. 1882,
 8, p. 467 211, p. 104
Note - this article incorporates content from Encyclopaedia Britannica, Eleventh Edition, (1910-1911)