Marggraf demonstrated that alumina was another constituent.
The oxide is a black or brown powder according as it is prepared from the exalate or sulphate, and when pure it is non-fluorescent, but mixed with gadolinia or alumina it possesses this property.
For example, at first he represented ferrous and ferric oxides by the formulae Fe02, Fe03, and by the analogy of zinc and other basic oxides he regarded these substances as constituted similarly to Fe02, and the acidic oxides alumina and chromium oxide as similar to FeO 3.
The raw materials used in the manufacture are: (I) iron-free kaolin, or some other kind of pure clay, which should contain its silica and alumina as nearly as possible in the proportion of 2SiO 2: Al203 demanded by the formula assigned to ideal kaolin (a deficit of silica, however, it appears can be made up for by addition of the calculated weight of finely divided silica); (2) anhydrous sulphate of soda; (3) anhydrous carbonate of soda; (4) sulphur (in the state of powder); and (5) powdered charcoal or relatively ash-free coal, or colophony in lumps.
The precipitated alumina is filtered off, the filtrate evaporated and the ammonium salt of the acid purified by recrystallization.
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.
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.
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.
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.
"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.
The precipitate, after having been collected and washed, is digested with a warm concentrated solution of ammonium carbonate, which dissolves the uranium as a yellow solution of ammonium uranate, while the hydrated oxide of iron, the alumina, &c., remain.
- Sheet-glass is almost wholly a soda-lime-silicate glass, containing only small quantities of iron, alumina and other impurities.
A good quality of sheet-glass should show, on analysis, a composition approximating to the following: silica (SiO 2), 72%; lime (CaO), 13%; soda (Na 2 O), 14%; and iron and alumina (Fe 2 O 3, Al 2 O 3), 1%.
Aluminium, when pure and kept out of contact with siliceous matter, is only oxidized at a white heat, and then very slowly, into alumina, Al 2 O 3.
The term clay is often used by chemists to denote hydrated silicate of alumina (Al 2 O 3 2SiO 2.2H 2 O), of which kaolin or china clay is a fairly pure form.
Alumina and lime, for example, which cannot be reduced at ordinary furnace temperatures, readily give up their oxygen to carbon in the electric furnace, and then combine with an excess of carbon to form metallic carbides.
The impossibility of working with just sufficient carbon to reduce the alumina, without using any excess which would be free to, ix.
A sheet iron case is then placed within the furnace, and the space between it and the walls rammed with limed charcoal; the interior is filled with fragments of the iron or copper to be alloyed, mixed with alumina and coarse charcoal, broken pieces of carbon being placed in position to connect the electrodes.
The reduction is not due to electrolysis, but to the action of carbon on alumina, a part of the carbon in the charge being consumed and evolved as carbon monoxide gas, which burns at the orifice in the cover so long as reduction is taking place.
Filtration in the chemical laboratory is commonly effected by the aid of a special kind of unsized paper, which in the more expensive varieties is practically pure cellulose, impurities like feric oxide, alumina, lime, magnesia and silica having been removed by treatment with hydrochloric and hydrofluoric acids.
Many of the oceanic islets are composed of coral limestone, which in this way becomes phosphatized; others are igneous, consisting of trachyte or basalt, and these rocks are also phosphatized on their surfaces but are not so valuable, inasmuch as the presence of iron or alumina in any quantity renders them unsuited for the preppration of artificial manures.
SAPPHIRE, 1 a blue transparent variety of corundum, or native alumina, much valued as a gem-stone.
Verneuil succeeded in imparting a sapphire-blue colour to artificial alumina by addition of i 5% of magnetic oxide of iron and o.
Chromium sesquioxide is a basic oxide, although like alumina it acts as an acid-forming oxide towards strong bases, forming salts called chromites.
In the later years of his life he applied himself to the problem of obtaining alumina in the crystalline form, and succeeded in making rubies identical with the natural gem not merely in chemical composition but also in physical properties.
But to ensure the permanence of structures in sea-water the great object is to choose a cement containing as little lime and alumina as possible, and free from sulphates such as gypsum; and more important still to proportion the sand and stones in the concrete in such a way that the structure is practically non-porous.
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.
He next devised a plan for manufacturing pure alumina from the natural ores, and finally elaborated a process and plant which held the field for almost thirty years.
Kaolin thus seems to be the best ore, and it would undoubtedly be used were it not for the fatal objection that no satisfactory process has yet been discovered for preparing pure alumina from any mineral silicate.
If, according to the present method of winning the metal, a bath containing silica as well as alumina is submitted to electrolysis, both oxides are dissociated, and as silicon is a very undesirable impurity, an alumina contaminated with silica is not suited for reduction.
Antrim, and have the advantage of being near the coast, so that the alumina can be transported by water-carriage.
After being dried at loo° C., Antrim bauxite contains from 33 to 60% of alumina, from 2 to 30% of ferric oxide, and from 7 to 24% of silica, the balance being titanic acid and water of combination.
The American bauxites contain from 38 to 67% of alumina, from 1 to 23% of ferric oxide, and from 1 to 32% of silica.
The French bauxites are of fairly constant composition, containing usually from 58 to 70% of alumina, 3 to 15% of foreign matter, and 27% made up of silica, iron oxide and water in proportions that vary with the colour and the situation of the beds.
Alumina itself is so refractory that it cannot be melted save by the oxyhydrogen blowpipe or the electric arc, and except in the molten state it is not susceptible of decomposition by any chemical reagent.
The first successful idea of using electricity depended on the enormous heating powers of the arc. The infusibility of alumina was no longer prohibitive, for the molten oxide is easily reduced by carbon.
Nevertheless, it was found impracticable to smelt alumina electrically except in presence of copper, so that the Cowles furnace yielded, not the pure metal, but an alloy.
It was soon discovered that the faculty of inducing dissociation possessed by the current might now be utilized with some hope of pecuniary success, but as electrolytic currents are of lower voltage than those required in electric furnaces, molten alumina again became impossible.
It has been found, however, that molten cryolite and the analogous double fluoride represented by the formula Al 2 F 6.2NaF are very efficient solvents of alumina, and that these solutions can be easily electrolysed at about 800° C. by means of a current that completely decomposes the oxide but leaves the haloid salts unaffected.
Molten cryolite dissolves roughly 30% of its weight of pure alumina, so that when ready for treatment the solution contains about the same proportion of what may be termed "available" aluminium as does the fused double chloride of aluminium and sodium.
Alumina dissolves readily enough in aqueous hydrochloric acid to yield a solution of the chloride, but neither this solution, nor that containing sodium chloride, can be evaporated to dryness without decomposition.
To obtain the anhydrous single or double chloride, alumina must be ignited with carbon in a current of chlorine, and to exclude iron from the finished metal, either the alumina must be pure or the chloride be submitted to purification.
In order to prepare pure alumina, bauxite and sodium carbonate were heated in a furnace until the reaction was complete; the product was then extracted with water to dissolve the sodium aluminate, the solution treated with carbon dioxide, and the precipitate removed and dried.
The residue, consisting of alumina and potassium sulphate, was leached with water to separate the insoluble matter which was dried as usual.
From this alumina the double chloride was prepared in essentially the same manner as practised at Salindres, but sundry economies accrued in the process, owing to the larger scale of working and to the adoption of W.
Of Oldbury was promoted to combine the advantages of Webster's alumina and Castner's sodium.
The operation was continuous, the metal being regularly run off from the bottom of the bath, while fresh alumina and flouride were added as required.
The original Deville process for obtaining pure alumina from bauxite was greatly simplified in 1889 by K.
The solution of sodium aluminate, containing aluminium oxide and sodium oxide in the molecular proportion of 6 to 1, is next agitated for thirty-six hours with a small quantity of hydrated alumina previously obtained, which causes the liquor to decompose, and some 70% of the aluminium hydroxide to be thrown down.
The filtrate, now containing roughly two molecules of alumina to one of soda, is concentrated to the original gravity of 1.45, and employed instead of fresh caustic for the attack of more bauxite; the precipitate is then collected, washed till free from soda, dried and ignited at about looo C. to convert it into a crystalline oxide which is less hygroscopic than the former amorphous variety.
By 1888 Hall was at work on a commercial scale at Pittsburg, reducing German alumina; in 1891 the plant was removed to New Kensington for economy in fuel, and was gradually enlarged to 150o h.p.; in 1894 a factory driven by water was erected at Niagara Falls, and subsequently works were established at Shawenegan in Canada and at Massena in the United States.
In 1895 the British Aluminium Company was founded to mine bauxite and manufacture alumina in Ireland, to prepare the necessary electrodes at Greenock, to reduce the aluminium by the aid of water-power at the Falls of Foyers, and to refine and work up the metal into marketable shapes at the old Milton factory of the Cowles Syndicate, remodelled to suit modern requirements.
The cell is filled up with cryolite, and the current is turned on till this is melted; then the pure powdered alumina is fed in continuously as long as the operation proceeds.
As a part of the voltage is consumed in the latter duty, only the residue can be converted into chemical work, and as the theoretical voltage of the aluminium fluoride in the cryolite is 4.0, provided the bath is kept properly supplied with alumina, the fluorides are not attacked.
The operation is essentially a dissociation of alumina into aluminium, which collects at the cathode, and into oxygen, which combines with the anodes to form carbon monoxide, the latter escaping and being burnt to carbon dioxide outside.
The molten metal has a specific gravity of 2 ï¿½ S4, that of molten cryolite saturated with alumina is 2.3 5, and that of the fluoride Al 2 F 6 2NaF saturated with alumina 1.97.
The latter therefore appears the better material, and was originally preferred by Hall; cryolite, however, dissolves more alumina, and has been finally adopted by both inventors.
Alumina is obtained as a white amorphous powder by heating aluminium hydroxide.
Crystallized alumina is also obtained by heating the fluoride with boron trioxide; by fusing aluminium phosphate with sodium sulphate; by heating alumina to a dull redness in hydrochloric acid gas under pressure; and by heating alumina with lead oxide to a bright red heat.
By drying at ordinary temperatures, the hydrate Al(OH) 3 ï¿½H 2 0 is obtained; at 300° this yields A10(OH), which on ignition gives alumina, Al 2 O 3.
Potassium aluminate, K 2 Al 2 0 4, is obtained in solution by dissolving aluminium hydrate in caustic potash; it is also obtained, as crystals containing three molecules of water, by fusing alumina with potash, exhausting with water, and crystallizing the solution in vacuo.
Sodium aluminate is obtained in the manufacture of alumina; it is used as a mordant in dyeing, and has other commercial applications.
Aluminium chloride, AlC1 3, was first prepared by Oersted, who heated a mixture of carbon and alumina in a current of chlorine, a method subsequently improved by Wohler, Bunsen, Deville and others.
Webster patented an improved process for making alumina, and the following year he organized the Aluminium Crown Metal Co.