Part of the sodium carbonate is recrystallised in order to purify it more thoroughly. In order to do this a saturated solution is left to crystallise at a temperature below 30° in a current of air, in order to promote the separation of the water vapour. The large transparent crystals (efflorescent in air) of Na2CO3,10H2O are then formed which have already been spoken of (Chapter [I].).
[14] The whole of the sulphur used in the production of the sulphuric acid employed in decomposing the common salt is contained in this residue. This is the great burden and expense of the soda works which use Leblanc's method. As an instructive example from a chemical point of view, it is worth while mentioning here two of the various methods of recovering the sulphur from the soda waste. Chance's process is treated in Chapter XX., Note 6.
Kynaston (1885) treats the soda waste with a solution (sp. gr. l·21) of magnesium chloride, which disengages sulphuretted hydrogen: CaS + MgCl2 + 2H2O = CaCl2 + Mg(OH)2 + H2S. Sulphurous anhydride is passed through the residue in order to form the insoluble calcium sulphite: CaCl2 + Mg(OH)2 + SO2 = CaSO3 + MgCl2 + H2O. The solution of magnesium chloride obtained is again used, and the washed calcium sulphite is brought into contact at a low temperature with hydrochloric acid (a weak aqueous solution) and hydrogen sulphide, the whole of the sulphur then separating:
CaSO3 + 2H2S + 2HCl = CaCl2 + 3H2O + 3S.
But most efforts have been directed towards avoiding the formation of soda waste.
[15] Among the drawbacks of the Leblanc process are the accumulation of ‘soda waste’ (Note [14]) owing to the impossibility at the comparatively low price of sulphur (especially in the form of pyrites) of finding employment for the sulphur and sulphur compounds for which this waste is sometimes treated, and also the insufficient purity of the sodium carbonate for many purposes. The advantages of the Leblanc process, besides its simplicity and cheapness, are that almost the whole of the acids obtained as bye-products have a commercial value; for chlorine and bleaching powder are produced from the large amount of hydrochloric acid which appears as a bye-product; caustic soda also is very easily made, and the demand for it increases every year. In those places where salt, pyrites, charcoal, and limestone (the materials required for alkali works) are found side by side—as, for instance, in the Ural or Don districts—conditions are favourable to the development of the manufacture of sodium carbonate on an enormous scale; and where, as in the Caucasus, sodium sulphate occurs naturally, the conditions are still more favourable. A large amount, however, of the latter salt, even from soda works, is used in making glass. The most important soda works, as regards the quantity of products obtained from them, are the English works.
As an example of the other numerous and varied methods of manufacturing soda from sodium chloride, the following may be mentioned: Sodium chloride is decomposed by oxide of lead, PbO, forming lead chloride and sodium oxide, which, with carbonic anhydride, yields sodium carbonate (Scheele's process). In Cornu's method sodium chloride is treated with lime, and then exposed to the air, when it yields a small quantity of sodium carbonate. In E. Kopp's process sodium sulphate (125 parts) is mixed with oxide of iron (80 parts) and charcoal (55 parts), and the mixture is heated in reverberatory furnaces. Here a compound, Na6Fe4S3, is formed, which is insoluble in water absorbs oxygen and carbonic anhydride, and then forms sodium carbonate and ferrous sulphide; this when roasted gives sulphurous anhydride, the indispensable material for the manufacture of sulphuric acid, and ferric oxide which is again used in the process. In Grant's method sodium sulphate is transformed into sodium sulphide, and the latter is decomposed by a stream of carbonic anhydride and steam, when hydrogen sulphide is disengaged and sodium carbonate formed. Gossage prepares Na2S from Na2SO4 (by heating it with carbon), dissolves it in water and subjects the solution to the action of an excess of CO2 in coke towers, thus obtaining H2S (a gas which gives SO2 under perfect combustion, or sulphur when incompletely burnt, Chapter XX., Note 6) and bicarbonate of sodium; Na2S + 2CO2 + 2H2O = H2S + 2HNaCO3. The latter gives soda and CO2 when ignited. This process quite eliminates the formation of soda-waste (see Note [3]) and should in my opinion be suitable for the treatment of native Na2SO4, like that which is found in the Caucasus, all the more since H2S gives sulphur as a bye-product.
Repeated efforts have been made in recent times to obtain soda (and chlorine, see Chapter II., Note [1]) from strong solutions of salt (Chapter X., Note [23 bis]) by the action of an electric current, but until now these methods have not been worked out sufficiently for practical use, probably partly owing to the complicated apparatus needed, and the fact that the chlorine given off at the anode corrodes the electrodes and vessels and has but a limited industrial application. We may mention that according to Hempel (1890) soda in crystals is deposited when an electric current and a stream of carbonic acid gas are passed through a saturated solution of NaCl.
Sodium carbonate may likewise be obtained from cryolite (Chapter XVII., Note 23) the method of treating this will be mentioned under Aluminium.
[16] This process (Chapter XVII.) was first pointed out by Turck, worked out by Schloesing, and finally applied industrially by Solvay. The first (1883) large soda factories erected in Russia for working this process are on the banks of the Kama at Berezniak, near Ousolia, and belong to Lubimoff. But Russia, which still imports from abroad a large quantity of bleaching powder and exports a large amount of manganese ore, most of all requires works carrying on the Leblanc process. In 1890 a factory of this kind was erected by P. K. Oushkoff, on the Kama, near Elagoubi.