see captionFig.78.—Continually-acting kiln for burning lime. The lime is charged from above and calcined by four lateral grates, R, M. D, fire-bars. B, space for withdrawing the burnt lime. K, stoke-house. M. fire grate. Q, R, under-grate.
Fig.78.—Continually-acting kiln for burning lime. The lime is charged from above and calcined by four lateral grates, R, M. D, fire-bars. B, space for withdrawing the burnt lime. K, stoke-house. M. fire grate. Q, R, under-grate.
Calcium oxide—that is, quicklime—is a substance (sp. gr. 3·15)which is unaffected by heat,[39]and may therefore serve as a fire-resisting material, and was employed by Deville for the construction of furnaces in which platinum was melted, and silver volatilised by the action of the heat evolved by the combustion of detonating gas. The hydrated lime, slaked lime, or calcium hydroxide, CaH2O2(specific gravity 2·07) is a most common alkaline substance, employed largely in building for making mortars or cements, in which case its binding property is mainly due to the absorption of carbonic anhydride.[40]Lime, like other alkalis, acts on many animal and vegetable substances, and for this reason has many practical uses—for example, for removing fats, and in agriculture for accelerating the decomposition of organic substances in the so-calledcompostsor accumulations of vegetable and animal remains used for fertilising land. Calcium hydroxide easily loses its water at a moderate heat (530°), but it does not part with water at 100°. When mixed with water, lime forms a pasty mass known asslaked limeand in a more dilute form asmilk of lime, because when shaken up in water it remains suspended in it for a long time and presents the appearance of a milky liquid. But, besides this, lime is directly soluble in water, not to any considerable extent, but still in such a quantity thatlime wateris precipitated by carbonic anhydride, and has clearly distinguishable alkaline properties. One part of lime requires at the ordinary temperature about 800 parts of water for solution. At 100° it requires about 1500 parts of water, and therefore lime-water becomes cloudy when boiled. If lime-water be evaporated in a vacuum, calcium hydroxide separates in six-sided crystals.[41]If lime-water be mixed with hydrogen peroxide minute crystals ofcalcium peroxide, CaO2,8H2O, separate; this compound is very unstable and, like barium peroxide, is decomposed by heat. Lime, as a powerful base, combines with all acids, and in this respect presents a transition from the true alkalis to magnesia. Many of the salts ofcalcium (the carbonate, phosphate, borate, and oxalate) are insoluble in water; besides which the sulphate is only sparingly soluble. As a more energetic base than magnesia, lime forms salts, CaX2, which are distinguished by their stability in comparison with the salts MgX2; neither does lime so easily form basic and double salts as magnesia.
Anhydrous lime does not absorb dry carbonic anhydride at the ordinary temperature. This was already known by Scheele, and Prof. Schuliachenko showed that there is no absorption even at 360°. It only proceeds at a red heat,[42]and then only leads to the formation of a mixture of calcium oxide and carbonate (Rose). But if the lime be slaked or dissolved, the absorption of carbonic anhydride proceeds rapidly and completely. These phenomena are connected with thedissociation of calcium carbonate, studied by Debray (1867) under the influence of the conceptions of dissociation introduced into science by Henri Saint-Claire Deville. Just as there is no vapour tension for non-volatile substances, so there is no dissociation tension of carbonic anhydride for calcium carbonate at the ordinarytemperature. Just as every volatile substance has a maximum possible vapour tension for every temperature, so also calcium carbonate has its correspondingdissociation tension; this at 770° (the boiling point of cadmium) is about 85 mm. (of the mercury column), and at 930° (the boiling point of Zn) it is about 520 mm. As, if the tension be greater, there will be no evaporation, so also there will he no decomposition. Debray took crystals of calc spar, and could not observe the least change in them at the boiling point of zinc (930°) in an atmosphere of carbonic anhydride taken at the atmospheric pressure (760 mm.), whilst on the other hand calcium carbonate may be completely decomposed at a much lower temperature if the tension of the carbonic anhydride be kept below the dissociation tension, which may be done either by directly pumping away the gas with an air-pump, or by mixing it with some other gas—that is, by diminishing the partial pressure of the carbonic anhydride,[43]just as an object may be dried at the ordinary temperature by removing the aqueous vapour or by carrying it off in a stream of another gas. Thus it is possible to obtain calcium carbonate from lime and carbonic anhydride at a certain temperature above that at which dissociation begins, and conversely to decompose calcium carbonate at the same temperature into lime and carbonic anhydride.[44]At the ordinary temperature the reaction of the first order (combination) cannot proceed because the second (decomposition, dissociation)cannot take place, and thus all the most important phenomena with respect to the behaviour of lime towards carbonic anhydride are explained by starting from one common basis.[45]
Calcium carbonate, CaCO3, is sometimes met with in nature in a crystalline form, and it forms an example of the phenomenon termeddimorphism—that is, it appears in two crystalline forms. When it exhibits combinations of forms belonging to the hexagonal system (six-sided prisms, rhombohedra, &c.) it is calledcalc spar. Calc spar has a specific gravity of 2·7, and is further characterised by a distinct cleavage along the planes of the fundamental rhombohedron having an angle of 105°. Perfectly transparent Iceland spar presents a clear example of double refraction (for which reason it is frequently employed in physical apparatus). The other form of calcium carbonate occurs in crystals belonging to the rhombic system, and it is then calledaragonite; its specific gravity is 3·0. If calcium carbonate be artificially produced by slow crystallisation at the ordinary temperature, it appears in the rhombohedral form, but if the crystallisation be aided by heat it then appears as aragonite. It may therefore be supposed that calc spar presents the form corresponding with a low temperature, and aragonite with a higher temperature during crystallisation.[46]
Calcium sulphatein combination with two equivalents of water, CaSO4,2H2O, is very widely distributed in nature, and is known asgypsum. Gypsum loses one and a half and two equivalents of water at a moderate temperature,[47]and anhydrous or burnt gypsum is then obtained, which is also known as plaster of Paris, and is employed in large quantities for modelling.[48]This use depends on the fact that burnt and finely-divided and sifted gypsum forms a paste when mixed with water; after a certain time this paste becomes slightly heated and solidifies, owing to the fact that the anhydrous calcium sulphate, CaSO4, again combines with water. When the plaster of Paris and water are first made into a paste they form a mechanical mixture, but when the mass solidifies, then a compound of the calcium sulphate with two molecules of water is produced; and this may be regarded as derived from S(OH)6by the substitution of two atoms of hydrogen by one atom of bivalent calcium. Natural gypsum sometimes appears as perfectly colourless, or variegated, marble-like, masses, and sometimes in perfectly colourless crystals,selenite, of specific gravity 2·33. The semi-transparent gypsum, oralabaster, is often carved into small statues. Besideswhich an anhydrous calcium sulphate, CaSO4, calledanhydrite(specific gravity 2·97), occurs in nature. It sometimes occurs along with gypsum. It is no longer capable of combining directly with water, and differs in this respect from the anhydrous salt obtained by gently igniting gypsum. If gypsum be very strongly heated it shrinks and loses its power of combining with water.[48 bis]One part of calcium sulphate requires at 0° 525 parts of water for solution, at 38° 466 parts, and at 100° 571 parts of water. The maximum solubility of gypsum is at about 36°, which is nearly the same temperature as that at which sodium sulphate is most soluble.[49]
As lime is a more energetic base than magnesia, socalcium chloride, CaCl2, is not so easily decomposed by water, and its solutions only disengage a small quantity of hydrochloric acid when evaporated, and when the evaporation is conducted in a stream of hydrochloric acid it easily gives an anhydrous salt which fuses at 719°; otherwise an aqueous solution yields a crystallo-hydrate, CaCl2,6H2O, which melts at 30°.[50]
Just as for potassium, K = 39 (and sodium, Na = 23), there are the near analogues, Rb = 85 and Cs = 133, and also another, Li = 7, so in exactly the same manner for calcium, Ca = 40 (and magnesium, Mg = 24), there is another analogue of lighter atomic weight, beryllium, Be = 9, besides the near analogues strontium, Sr = 87, and barium, Ba = 137. As rubidium and cæsium are more rarely met with in nature than potassium, so also strontium and barium are rarer than calcium (in the same way that bromine and iodine are rarer than chlorine). Since they exhibit many points of resemblance with calcium, strontium and barium may be characterised after a very short acquaintance with their chief compounds; this shows the important advantages gained by distributing the elements according to their natural groups, to which matter we shall turn our attention in the next chapter.
Among the compounds of barium met with in nature the commonest is thesulphate, BaSO4, which forms anhydrous crystals of the rhombic system, which are identical in their crystalline form with anhydrite, and generally occur as transparent and semi-transparent masses of tabular crystals having a high specific gravity, namely 4·45, for which reason this salt bears the name ofheavy sparorbarytes. Analogous to it iscelestine, SrSO4, which is, however, more rarely met with. Heavy spar frequently forms the gangue separated on dressing metallic ores from the vein stuff; this mineral is the source of all other barium compounds; for the carbonate, although more easily transformed into the other compounds (because acids act directly on it, evolving carbonic anhydride), is a comparatively rare mineral (BaCO3forms the mineralwitherite; SrCO3,strontianite; both are rare, the latter is found at Etna). The treatment of barium sulphate is rendered difficult from the fact that it is insoluble both in water and acids, and has therefore to be treated by a method of reduction.[51]Like sodium sulphate and calcium sulphate, heavy spar when heated with charcoal parts with its oxygen and forms barium sulphide, BaS. For this purpose a pasty mixture of powdered heavy spar, charcoal, and tar is subjected to the action of a strong heat, when BaSO4+ 4C = BaS + 4CO. The residue is then treated with water, in which the barium sulphide is soluble.[52]When boiled with hydrochloric acid,barium chloride, BaCl2, is obtained in solution, and the sulphur is disengaged as gaseous sulphuretted hydrogen, BaS + 2HCl = BaCl2+ H2S. In this manner barium sulphate is converted into barium chloride,[53]and the latter by double decomposition with strong nitric acid or nitre gives the less soluble barium nitrate, Ba(NO3)2,[54]or with sodiumcarbonate a precipitate of barium carbonate, BaCO3. Both these salts are able to givebarium oxide, orbaryta, BaO, and the hydroxide, Ba(HO)2, which differs from lime by its great solubility in water,[55]and by the ease with which it forms a crystallo-hydrate, BaH2O2,8H2O, from its solutions. Owing to its solubility, baryta is frequently employed in manufactures and in practical chemistry as an alkali which has the very important property that it may be always entirely removed from solution by the addition of sulphuric acid, which entirely separates it as the insoluble barium sulphate, BaSO4. It may also be removed whilst it remains in an alkaline state (for example, the excess which may remain when it is used for saturating acids) by means of carbonic anhydride, which also completely precipitates baryta as a sparingly soluble, colourless, and powdery carbonate. Both these reactions show that baryta has such properties as would very greatly extend its use were its compounds as widely distributed as those of sodium and calcium, and were its soluble compounds not poisonous. Barium nitrate is directly decomposed by the action of heat, barium oxide being left behind. The same takes place with barium carbonate, especially that form of it precipitated from solutions, and when mixed with charcoal or ignited in an atmosphere of steam. Barium oxide combines with water with the development of a large amount of heat, and the resultant hydroxide is very stable in its retention of the water, although it parts with it when strongly ignited.[55 bis]With oxygen the anhydrous oxide gives, as already mentioned inChaptersIII. andIV., aperoxide, BaO2.[56]Neither calcium nor strontium oxides are able to give such a peroxide directly, but they form peroxides under the action of hydrogen peroxide.
Barium oxide is decomposed when heated with potassium; fused barium chloride is decomposed, as Davy showed, by the action of a galvanic current, forming metallicbarium; and Crookes (1862) obtained an amalgam of barium from which the mercury could easily be driven off, by heating sodium amalgam in a saturated solution of barium chloride. Strontium is obtained by the same processes. Both metals are soluble in mercury, and seem to be non-volatile or only very slightly volatile. They are both heavier than water; the specific gravity of barium is 3·6, and of strontium 2·5. They both decompose water at the ordinary temperature, like the metals of the alkalis.
Barium and strontium as saline elements are characterised by their powerful basic properties, so that they form acid salts with difficulty, and scarcely form basic salts. On comparing them together and with calcium, it is evident that the alkaline properties in this group (as in the group potassium, rubidium, cæsium) increase with the atomic weight, and this succession clearly shows itself in many of their corresponding compounds. Thus, for instance, the solubility of the hydroxides RH2O2and the specific gravity[57]rise in passing from calcium to strontium and barium, while the solubility of the sulphatesdecreases,[58]and therefore in the case of magnesium and beryllium, as metals whose atomic weights are still less, we should expect the solubility of the sulphates to be greater, and this is in reality the case.
Just as in the series of the alkali metals we saw the metals potassium, rubidium, and cæsium approaching near to each other in their properties, and allied to them two metals having smaller combining weights—namely, sodium, and the lightest of all, lithium, which all exhibited certain peculiar characteristic properties—so also in the case of the metals of the alkaline earths we find, besides calcium, barium, and strontium, the metal magnesium and alsoberylliumorglucinum. In respect to the magnitude of its atomic weight, this last occupies the same position in the series of the metals of the alkaline earths as lithium does in the series of the alkali metals, for the combining weight of beryllium, Be or Gl = 9. This combining weight is greater than that of lithium (7), as the combining weight of magnesium (24) is greater than that of sodium (23), and as that of calcium (40) is greater than that of potassium (39), &c.[59]Beryllium was so named because it occurs in the mineralberyl. The metal is also called glucinum (from the Greek word γλυκύς, ‘sweet’), because its salts have a sweet taste. It occurs in beryl, aquamarine, the emerald, and other minerals, which are generally of a green colour; they are sometimes found in considerable masses, but as a rule are comparatively rare and, as transparent crystals, form precious stones. The composition of beryl and of the emerald is as follows: Al2O3,3BeO,6SiO2. The Siberian and Brazilian beryls are the best known. The specific gravity of beryl is about 2·7. Beryllium oxide, from the feebleness of its basic properties, presentsan analogy to aluminium oxide in the same way that lithium oxide is analogous to magnesium oxide.[60]Owing to its rare occurrence in nature, to the absence of any especially distinct individual properties, and to the possibility of foretelling them to a certain extent on the basis of the periodic system of the elements given in the following chapter, and owing to the brevity of this treatise, we will not discuss at any length the compounds of beryllium, and will only observe that their individuality was pointed out in 1798 by Vauquelin, and that metallic beryllium was obtained by Wöhler and Bussy. Wöhler obtainedmetallic beryllium(like magnesium) by acting on beryllium chloride, BeCl2, with potassium (it is best prepared by fusing K2BeF4with Na). Metallic beryllium has a specific gravity 1·64 (Nilson and Pettersson). It is very infusible, melting at nearly the same temperature as silver, which it resembles in its white colour and lustre. It is characterised by the fact that it is very difficultly oxidised, and even in the oxidising flame of the blowpipe is only superficially covered by a coating of oxide; it does not burn in pure oxygen, and does not decompose water at the ordinary temperature orat a red heat, but gaseous hydrochloric acid is decomposed by it when slightly heated, with evolution of hydrogen and development of a considerable amount of heat. Even dilute hydrochloric acid acts in the same manner at the ordinary temperature. Beryllium also acts easily on sulphuric acid, but it is remarkable that neither dilute nor strong nitric acid acts on beryllium, which seems especially able to resist oxidising agents. Potassium hydroxide acts on beryllium as on aluminium, hydrogen being disengaged and the metal dissolved, but ammonia has no action on it. These properties of metallic beryllium seem to isolate it from the series of the other metals described in this chapter, but if we compare the properties of calcium, magnesium, and beryllium we shall see that magnesium occupies a position intermediate between the other two. Whilst calcium decomposes water with great ease, magnesium does so with difficulty, and beryllium not at all. The peculiarities of beryllium among the metals of the alkaline earths recall the fact that in the series of the halogens we saw that fluorine differed from the other halogens in many of its properties and had the smallest atomic weight. The same is the case with regard to beryllium among the other metals of the alkaline earths.
In addition to the above characteristics of the compounds of the metals of the alkaline earths, we must add that they, like the alkali metals, combine with nitrogen and hydrogen, and while sodium nitride (obtained by igniting the amide of sodium, Chapter XII., Note44 bis) and lithium nitride (obtained by heating lithium in nitrogen, Chapter XIII., Note39) have the composition R3N, so the nitrides of magnesium (Note14), calcium, strontium, and barium have the composition R3N2, for example, Ba3N2, as might be expected from the diatomicity of the metals of the alkaline earths and from the relation of the nitrides to ammonia, which is obtained from all of these compounds by the action of water. Thenitridesof Ca, Sr, and Ba are formed directly (Maquenne, 1892) by heating the metals in nitrogen. They all have the appearance of an amorphous powder of dark colour; as regards their reactions, it is known that besides disengaging ammonia with water, they form cyanides when heated with carbonic oxide; for instance, Ba3N2+ 2CO = Ba(CN)2+ 2BaO.[61]
The metals of the alkaline earths, just like Na and K, absorb hydrogen under certain conditions, and form pulverulent easily oxidisable metallic hydrides, whose composition corresponds exactly to that of Na2H and K2H, with the substitution of K2and Na2by the atomsBe, Mg, Ca, Sr, and Ba. Thehydrides of the metals of the alkaline earthswere discovered by C. Winkler (1891) in investigating the reducibility of these metals by magnesium. In reducing their oxides by heating them with magnesium powder in a stream of hydrogen, Winkler observed that the hydrogen was absorbed (but very slowly),i.e.at the moment of their separation all the metals of the alkaline earths combine with hydrogen. This absorptive power increases in passing from Be to Mg, Ca, Sr, and Ba, and the resultant hydrides retain the combined hydrogen[62]when heated, so that these hydrides are distinguished for their considerable stability under heat, but they oxidise very easily.[63]
Thus the analogies and correlation of the metals of these two groups are now clearly marked, not only in their behaviour towards oxygen, chlorine, acids, &c., but also in their capability of combining with nitrogen and hydrogen.