The Principles of Chemistry, Volume I

by Dmitry Ivanovich Mendeleyev

[16 bis] Mond (see Chapter XI., Note [3 bis]) separates the NH₄Cl from the residual solutions by cooling (Chapter X., Note [44]); ignites the sal-ammoniac and passes the vapour over MgO, and so re-obtains the NH₃, and forms MgCl₂: the former goes back for the manufacture of soda, while the latter is employed either for making HCl or Cl₂.

[17] Commercial soda ash (calcined, anhydrous) is rarely pure; the crystallised soda is generally purer. In order to purify it further, it is best to boil a concentrated solution of soda ash until two-thirds of the liquid remain, collect the soda which settles, wash with cold water, and then shake up with a strong solution of ammonia, pour off the residue, and heat. The impurities will then remain in the mother liquors, &c.

Some numerical data may be given for sodium carbonate. The specific gravity of the anhydrous salt is 2·48, that of the decahydrated salt 1·46. Two varieties are known of the heptahydrated salt (Löwel, Marignac, Rammelsberg), which are formed together by allowing a saturated solution to cool under a layer of alcohol; the one is less stable (like the corresponding sulphate) and at 0° has a solubility of 32 parts (of anhydrous salt) in 100 water; the other is more stable, and its solubility 20 parts (of anhydrous salt) per 100 of water. The solubility of the decahydrated salt in 100 water = at 0°, 7·0; at 20°, 21·7; at 30°, 37·2 parts (of anhydrous salt). At 80° the solubility is only 46·1, at 90° 45·7, at 100°, 45·4 parts (of anhydrous salt). That is, it falls as the temperature rises, like Na₂SO₄. The specific gravity (Note [7]) of the solutions of sodium carbonate, according to the data of Gerlach and Kohlrausch, at 15°/4° is expressed by the formula, s = 9,992 + 104·5p + 0·165p². Weak solutions occupy a volume not only less than the sum of the volumes of the anhydrous salt and the water, but even less than the water contained in them. For instance, 1,000 grams of a 1 p.c. solution occupy (at 15°) a volume of 990·4 c.c. (sp. gr. 1·0097), but contain 990 grams of water, occupying at 15° a volume of 990·8 c.c. A similar case, which is comparatively rare occurs also with sodium hydroxide, in those dilute solutions for which the factor A is greater than 100 if the sp. gr. of water at 4° = 100,000, and if the sp. gr. of the solution be expressed by the formula S = S₀ + Ap + Bp², where S₀ is the specific gravity of the water. For 5 p.c. the sp. gr. 15°/4° = 1·0520; for 10 p.c. 1·1057; for 15 p.c. 1·1603. The changes in the sp. gr. with the temperature are here almost the same as with solutions of sodium chloride with an equal value of p.

[18] The resemblance is so great that, notwithstanding the difference in the molecular composition of Na₂SO₄ and Na₂CO₃, they ought to be classed under the type (NaO)₂R, where R = SO₂ or CO. Many other sodium salts also contain 10 mol. H₂O.

[19] According to the observations of Pickering. According to Rose, when solutions of sodium carbonate are boiled a certain amount of carbonic anhydride is disengaged.

[20] The composition of this salt, however, may be also represented as a combination of carbonic acid, H₂CO₃, with the normal salt, Na₂CO₃, just as the latter also combines with water. Such a combination is all the more likely because (1) there exists another salt, Na₂CO₃,2NaHCO₃,2H₂O (sodium sesquicarbonate), obtained by cooling a boiling solution of sodium bicarbonate, or by mixing this salt with the normal salt; but the formula of this salt cannot be derived from that of normal carbonic acid, as the formula of the bicarbonate can. At the same time the sesqui-salt has all the properties of a definite compound; it crystallises in transparent crystals, has a constant composition, its solubility (at 0° in 100 of water, 12·6 of anhydrous salt) differs from the solubility of the normal and acid salts; it is found in nature, and is known by the names of trona and urao. The observations of Watts and Richards showed (1886) that on pouring a strong solution of the acid salt into a solution of the normal salt saturated by heating, crystals of the salt NaHCO₃,Na₂CO₃,2H₂O may be easily obtained, as long as the temperature is above 35°. The natural urao (Boussingault) has, according to Laurent, the same composition. This salt is very stable in air, and may be used for purifying sodium carbonate on the large scale. Such compounds have been little studied from a theoretical point of view, although particularly interesting, since in all probability they correspond with ortho-carbonic acid, C(OH)₄, and at the same time correspond with double salts like astrakhanite (Chapter XIV., Note [25]). (2) Water of crystallisation does not enter into the composition of the crystals of the acid salt, so that on its formation (occurring only at low temperatures, as in the formation of crystalline compounds with water) the water of crystallisation of the normal salt separates and the water is, as it were, replaced by the elements of carbonic acid. If anhydrous sodium carbonate be mixed with the amount of water requisite for the formation of Na₂CO₃,H₂O, this salt will, when powdered, absorb CO₂ as easily at the ordinary temperature as it does water.

[21] 100 parts of water at 0° dissolve 7 parts of the acid salt, which corresponds with 4·3 parts of the anhydrous normal salt, but at 0° 100 parts of water dissolve 7 parts of the latter. The solubility of the bi- or acid salt varies with considerable regularity; 100 parts of water dissolves at 15° 9 parts of the salt, at 30° 11 parts.

The ammonium, and more especially the calcium, salt, is much more soluble in water. The ammonia process (see p. [524]) is founded upon this. Ammonium bicarbonate (acid carbonate) at 0° has a solubility of 12 parts in 100 water, at 30° of 27 parts. The solubility therefore increases very rapidly with the temperature. And its saturated solution is more stable than a solution of sodium bicarbonate. In fact, saturated solutions of these salts have a gaseous tension like that of a mixture of carbonic anhydride and water—namely, at 15° and at 50°, for the sodium salt 120 and 750 millimetres, for the ammonium salt 120 and 563 millimetres. These data are of great importance in understanding the phenomena connected with the ammonia process. They indicate that with an increased pressure the formation of the sodium salt ought to increase if there be an excess of ammonium salt.

[22] Crystalline sodium carbonate (broken into lumps) also absorbs carbonic anhydride, but the water contained in the crystals is then disengaged: Na₂CO₃,10H₂O + CO₂ = Na₂CO₃,H₂CO₃ + 9H₂O, and dissolves part of the carbonate; therefore part of the sodium carbonate passes into solution together with all the impurities. When it is required to avoid the formation of this solution, a mixture of ignited and crystalline sodium carbonate is taken. Sodium bicarbonate is prepared chiefly for medicinal use, and is then often termed carbonate of soda, also, for instance, in the so-called soda powders, for preparing certain artificial mineral waters, for the manufacture of digestive lozenges like those made at Essentuki, Vichy, &c.

[23] In chemistry, sodium oxide is termed ‘soda,’ which word must be carefully distinguished from the word sodium, meaning the metal.