When the aluminous lixivia contain a great deal of sulphate of iron, it may be good policy to withdraw a portion of it by crystallisation before precipitating the alum. With this view, the liquors must be evaporated to the density of 1·4, and then run off into crystallising stone cisterns. After the green vitriol has concreted, the liquor should be pumped back into the evaporating pan, and again brought to the density of 1·4. On adding to it, now, the alkaline precipitants, the alum will fall down from this concentrated solution, in a very minute crystalline powder, very easy to wash and purify. But this method requires more vessels and manipulation than the preceding, and should only be had recourse to from necessity; since it compels us to carry on the manufacture of both the valuable alum and the lower priced salts at the same time; moreover, the copperas extracted at first from the schist liquors carries with it, as we have said, a portion of the sulphate of alumina, and acquires thereby a dull aspect; whereas the copperas obtained after the separation of the alum is of a brilliant appearance.
5. The washing, or edulcoration, of the Alum Powder.—This crystalline pulverulent matter has a brownish colour, from the admixture of the ferruginous liquors; but it may be freed from it by washing with very cold water, which dissolves not more than one sixteenth of its weight of alum. After stirring the powder and the water well together, the former must be allowed to settle, and then the washing must be drawn off. A second washing will render the alum nearly pure. The less water is employed, and the more effectually it is drained off, the more complete is the process. The second water may be used in the first washing of another portion of alum powder, in the place of pure water. These washings may be added to the schist lixivia.
6. The crystallisation.—The washed alum is put into a lead pan, with just enough water to dissolve it at a boiling heat; fire is applied, and the solution is promoted by stirring. Whenever it is dissolved in a saturated state, it is run off into the crystallising vessels, which are called roching casks. These casks are about five feet high, three feet wide in the middle, somewhat narrower at the ends; they are made of very strong staves, nicely fitted to each other, and held together by strong iron hoops, which are driven on pro tempore, so that they may be easily knocked off again, in order to take the staves asunder. The concentrated solution, during its slow cooling in these close vessels, forms large regular crystals, which hang down from the top, and project from the sides, while a thick layer or cake lines the whole interior of the cask. At the end of eight or ten days, more or less, according to the weather, the hoops and staves are removed, when a cask of apparently solid alum is disclosed to view. The workman now pierces this mass with a pickaxe at the side near the bottom, and allows the mother water of the interior to run off on the sloping stone floor into a proper cistern, whence it is taken and added to another quantity of washed powder to be crystallised with it. The alum is next broken into lumps, exposed in a proper place to dry, and is then put into the finished bing for the market. There is sometimes a little insoluble basic alum (subsulphate) left at the bottom of the cask. This being mixed with the former mother liquors, gets sulphuric acid from them; or, being mixed with a little sulphuric acid, it is equally converted into alum.
When, instead of potash or its salts, the ammoniacal salts are used, or putrid urine, with the aluminous lixivia, ammoniacal alum is produced, which is perfectly similar to the potash alum in its appearance and properties. At a gentle heat both lose their water of crystallisation, amounting to 451⁄2 per cent. for the potash alum, and 48 for the ammoniacal. The quantity of acid is the same in both, as, also, very nearly the quantity of alumina, as the following analyses will show:
| Potash alum. | Ammonia alum. | ||
| Sulphate of potash | 18·34 | Sulphate of ammonia | 12·88 |
| Sulphate of alumina | 36·20 | Sulphate of alumina | 38·64 |
| Water | 45·46 | Water | 48·48 |
| 100·00 | 100·00 | ||
| Or otherwise, Potash alum. | Ammonia alum. | ||
| 1 atom sulphate of potash | 1089·07 | 1 atom sulphate of ammonia | 716·7 |
| 1 atom sulphate of alumina | 2149·80 | 1 atom sulphate of alumina | 2149·8 |
| 24 water | 2669·52 | 24 water | 2699·5 |
| 5938·39 | 5566·0 | ||
| Or, Potash alum. | Ammonia alum. | ||
| Alumina | 10·82 | Alumina | 11·90 |
| Potash | 9·94 | Ammonia | 3·89 |
| Sulphuric Acid | 33·77 | Sulphuric acid | 36·10 |
| Water | 45·47 | Water | 48·11 |
| 100·00 | 100·00 | ||
When heated pretty strongly, the ammoniacal alum loses its sulphuric acid and ammonia, and only the earth remains. This is a very convenient process for procuring pure alumina. Ammoniacal alum is easily distinguished from the other by the smell of ammonia which it exhales when triturated with quicklime. The Roman alum, made from alum stone, possesses most of the properties of the schist-made alums, but it has a few peculiar characters: it crystallises always in opaque cubes, whereas the common alum crystallises in transparent octahedrons. It is probable that Roman alum is a sulphate of alumina and potash, with a slight excess of the earthy ingredient. It is permanent when dissolved in cold water; for after a slow evaporation it is recovered in a cubical form. But when it is dissolved in water heated to 110° Fahr. and upwards, or when its solution is heated above this pitch, subsulphate of alumina falls, and on evaporation octahedral crystals of common alum are obtained. The exact composition of the Roman alum has not been determined, as far as I know. It probably differs from the other also in its water of crystallisation. The Roman alum contains, according to MM. Thenard and Roard, only 1⁄2200 of sulphate of iron, while the common commercial alums contain 1⁄1000. It may be easily purified by solution, granulation, crystallisation, and washing, as has been already explained.
Alum is made extensively in France from an artificial sulphate of alumina. For this purpose clays are chosen as free as possible from carbonate of lime and oxide of iron. They are calcined in a reverberatory furnace, in order to expel the water, to peroxidise the iron, and to render the alumina more easily acted on by the acid. The expulsion of the water renders the clay porous and capable of absorbing the sulphuric acid by capillary attraction. The peroxidation of the iron renders it less soluble in the sulphuric acid; and the silica of the clay, by reacting on the alumina, impairs its aggregation, and makes it more readily attracted by the acid. The clay should, therefore, be moderately calcined; but not so as to indurate it like pottery ware, for it would then suffer a species of siliceous combination which would make it resist the action of acids. The clay is usually calcined in a reverberatory furnace, the flame of which serves thereafter to heat two evaporating pans and a basin for containing a mixture of the calcined clay and sulphuric acid. As soon as the clay has become friable in the furnace it is taken out, reduced to powder, and passed through a fine sieve. With 100 parts of the pulverised clay, 45 parts of sulphuric acid, of sp. gr. 1·45, are well mixed, in a stone basin, arched over with brickwork. The flame and hot air of a reverberatory furnace are made to play along the mixture, in the same way as described for evaporating the schist liquors. See [Soda]. The mixture, being stirred from time to time, is, at the end of a few days, to be raked out, and to be set aside in a warm place, for the acid to work on the clay, during six or eight weeks. At the end of this time it must be washed, to extract the sulphate of alumina. With this view, it may be treated like the roasted alum ores above described. If potash alum is to be formed, this sulphate of alumina is evaporated to the specific gravity of 1·38; but if ammonia alum, to the specific gravity of only 1·24; because the sulphate of ammonia, being soluble in twice its weight of water, will cause a precipitation of pulverulent alum from a weaker solution of sulphate of alumina than the less soluble sulphate of potash could do.
The alum stone, from which the Roman alum is made, contains potash. The following analysis of alunite, by M. Cordier, places this fact in a clear light:—
| Sulphate of potash | 18·53 |
| Sulphate of alumina | 38·50 |
| Hydrate of alumina | 42·97 |
| 100·00 | |
To transform this compound into alum, it is merely necessary to abstract the hydrate of alumina. The ordinary alum stone, however, is rarely so pure as the above analysis would seem to show; for it contains a mixture of other substances; and the above are in different proportions.