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The first will contain very little potassium chloride, and the latter very little sodium chloride. But if we take, for example, a mixture of solutions of magnesium sulphate and zinc sulphate, they cannot be separated from each other by evaporating the mixture, notwithstanding the rather considerable difference in the solubility of these salts. Again, the isomorphous salts, magnesium carbonate, and calcium carbonate are found together--that is, in one crystal-in nature. The angle of the rhombohedron of these magnesia-lime spars is intermediate between the angles proper to the two spars individually (for calcium carbonate, the angle of the rhombohedron is 105° 8'; magnesium carbonate, 107° 30' ; CaMg(CO3)2, 106° 10'). Certain of these isomorphous mixtures of calcand magnesia spars appearin well-formed crystals, and in this case there not unfrequently exists a simple molecular proportion of strictly definite chemical combination between the component salts-for instance, CaCO3,MgCO3--whilst in other cases, especially in the absence of distinct crystallisation (in dolomites), no such simple molecular proportion is observable: this is also the case in many artificially prepared isomorphous mixtures. The microscopical and crystallo.optical researches of Professor Inostrantzoff and others show that in many cases there is really a mechanical, although microscopically minute, juxtaposition in one whole of the heterogeneous crystals of calcium carbonate (double refracting) and of the compound CaMgC,0. If we suppose the adjacent parts to be microscopically small (on the basis of the researches of Mallard, Weruboff, and others), we obtain an idea of isomorphous mixtures. A formula of the following kind is given to isomorphous mixtures : for instance, for spars, RCO3, where R=Mg, Ca, and where it may be Fe, Mn . . ., &c. This means that the Ca is partially replaced by Mg or another metal. Alums form a common example of the separation of isomorphous mixtures from solutions. They are double sulphates (or seleniates) of alumina (or oxides isomorphous with it) and the alkalis, which crystallise in well-formed crystals. If aluminium sulphate be mixed with potassium sulphate, an alum separates, having the composition KAIS,0,,121,0. If sodium sulphate or ammonium sulphate, or rubidium (or thallium) sulphate be used, we obtain alums having the composition RAIS,O,,12H,O. Not only do they all crystallise in the cubic system, but they also contain an equal atomic quantity of water of crystallisation (12H,0). Besides which, if we mix solutions of the potassium and ammonium (NH,AIS,O,,12H,0) alums together, then the crystals which separate will contain various proportions of the alkalis taken, and separate crystals of the alums of one or the other kind will not be obtained, but each separate crystal will contain both potassium and ammonium. Nor is this all ; if we take a crystal of a potassium alum and immerse it in a solution capable of yielding ammonia alum, the crystal of the potash alum will continue to grow and increase in size in this solution--that is, a layer of the ammonia or other alum will deposit itself upon the planes bounding the crystal of the potash alum. This is very distinctly seen if a colourless crystal of a common alum be immersed in a saturated violet solution of chrome alum, K Crs,O3,12H,O, which then deposits itself in a violet layer over the colourless crystal of the alumina alum, as was observed even before Mitscherlich noticed it. If this crystal be then immersed in a solution of an alumina alum, a layer of this salt will form over the layer of chrome alum, so that one alum is able to incite the growth of the other. If the deposition proceed simultaneously, the resultant intermixture may be minute and inseparable, but its nature is understood from the preceding experiments ; the attractive force of crystallisation of isomorphous substances is so nearly equal that the attractive power of an isomorphous substance induces a crystalline superstructure exactly the same as would be produced by the attractive force of like crystalline particles. From this it is evident that one isomorphous substance may induce the crystallisation 4 of another. Such a phenomenon explains, on the one hand, the aggregation of different isomorphous substances in one crystal, whilst, on the other hand, it serves as a most exact indication of the nearness both of the molecular composition of isomorphous substances and of those forces which are proper to the elements which distinguish the isomorphous substances. Thus, for example, ferrous sulphate or green vitriol crystallises in the monoclinic system and contains seven molecules of water, FeSO,,7H,O, whilst copper vitriol crystallises with five molecules of water in the triclinic system, CuSO4,51,0; nevertheless, it may be easily proved that both salts are perfectly isomorphous ; that they are able to appear in identically the same forms and with an equal molecular amount of water. For instance, Marignac, by evaporating a mixture of sulphuric acid and ferrous sulphate under the receiver of an air-pump, first obtained crystals of the hepta-hydrated salt, and then of the penta-hydrated salt FeSO4,5H,O, which were perfectly similar to the crystals of copper sulphate. Furthermore, Lecoq de Boisbaudran, by immersing crystals of FeSO4, 7H,0 in a supersaturated solution of copper sulphate, caused the latter to deposit in the same form as ferrous sulphate, in crystals of the monoclinic system, CuSO4.7H2O.
3 The cause of the difference which is observed in different compounds of the same type, with respect to their property of forming isomorphous mixtures, must not be looked for in the difference of their volumetric composition, as many investigators, including Kopp, affirm. The molecular volumes (found by dividing the molecular weight by the density) of those isomorphous substances which do give intermixtures are not nearer to each other than the volumes of those which do not give mixtures; for example, for magnesium carbonate the combining weight is 84, density 3:06, and volume therefore 27; for calcium carbonate in the form of cale spar the volume is 37, and in the form of aragonite 33; for strontium carbonate 41, for barium carbonate 46; that is, the volume of these closely allied isomorphous substances increases with the combining weight. The same is observed if we compare sodium chloride (molecular volume=27) with potassium chloride (volume = 37), or sodium sulphate (volume = 55) with potassium sulphate (volume=66), or sodium nitrate 39 with potassium nitrate 48, although the latter are less capable of giving isomorphous mixtures than the former. It is evident that the cause of isomorphism cannot be explained by an approximation in molecular volumes. It is more likely that, given a similarity in form and composition, the faculty to give isomorphous mixtures is connected with the laws and degree of solubility.
4 A phenomenon of a similar kind is shown for magnesium sulphate in Note 27 of the last chapter. In the same example we see what a complication the phenomena of dimorphism may introduce when the forms of analogous compounds are compared.
Hence it is evident that isomorphism--that is, the analogy of forms and the property of inducing crystallisation-may serve as a means for the discovery of analogies in molecular composition. We will take an example in order to render this clear. If, instead of aluminium sulphate, we add magnesium sulphate to potassium sulphate, then, on evaporating the solution, the double salt K., MgS,O,6,0 (Chapter XIV., Note 28) separates instead of an alum, and the ratio of the component parts (in alums one atom of potassium per 2804, and here two atoms) and the amount of water of crystallisation (in alums 12, and here 6 equivalents per 2804) are quite different ; nor is this double salt in any way isomorphous with the alums, nor capable of forming an isomorphous crystalline mixture with them, nor does the one salt provoke the crystallisation of the other. From this we must conclude that although alumina and magnesia, or aluminium and magnesium, resemble each other, they are not isomorphous, and that although they give partially similar double salts, these salts are not analogous to each other. And this is expressed in their chemical formulæ by the fact that the number of atoms in alumina or aluminium oxide, A1,03, is different from the number in magnesia, MgO. Aluminium is trivalent and magnesium bivalent. Thus, having obtained a double salt from a given metal, it is possible to judge of the analogy of the given metal with aluminium or with magnesium, or of the absence of such an analogy, from the composition and form of this salt. Thus zinc, for example, does not form alums, but forms a double salt with potassium sulphate, which has a composition exactly like that of the corresponding salt of magnesium. It is often possible to distinguish the bivalent metals analogous to magnesium or calcium from the trivalent metals, like aluminium, by such a method. Furthermore, the specific heat and vapour density serve as guides. There are
also indirect proofs. Thus iron gives ferrous compounds, FeX.,, which are isomorphous with the compounds of magnesium, and ferric compounds, FeX3, which are isomorphous with the compounds of aluminium ; in this instance the relative composition is directly determined by analysis, because, for a given amount of iron, FeCl2 only contains two-thirds of the amount of chlorine which occurs in FeCl3, and the composition of the corresponding oxygen compounds, i.e. of ferrous oxide, FeO, and ferric oxide, Fe,O3, clearly indicates the analogy of the ferrous oxide with MgO and of the ferric oxide with Al,03.
Thus in the building up of similar molecules in crystalline forms we see one of the numerous means for judging of the internal world of molecules and atoms, and one of the weapons for conquests in the invisible world of molecular mechanics which forms the main object of physico-chemical knowledge. This method • has more than once been
5 The property of solids of occurring in regular crystalline forms—the occurrence of many substances in the earth's crust in these forms--and those geometrical and simple laws which govern the formation of crystals long ago attracted the attention of the naturalist to crystals. The crystalline form is, without doubt, the expression of the relation in which the atoms occur in the molecules, and in which the molecules occur in the mass, of a substance. Crystallisation is determined by the distribution of the molecules along the direction of greatest cohesion, and therefore those forces must take part in the crystalline distribution of matter which act between the molecules; and, as they depend on the forces binding the atoms together in the molecules, a very close connection must exist between the atomic composition and the distribution of the atoms in the molecule on the one hand, and the crystalline form of a substance on the other hand ; and hence an insight into the composition may be arrived at from the crystalline form. Such is the elementary and a priori idea which lies at the base of all researches into the connection between composition and crystalline form. Haiiy in 1811 established the following fundamental law, which has been worked out by later investigators: That the fundamental crystalline form for a given chemical compound is constant (only the combinations vary), and that with a change of composition the crystalline form also changes, naturally with the exception of such limiting forms as the cube, regular octahedron, &c., which may belong to various substances of the regular system. The fundamental form is determined by the angles of certain fundamental geometric forms (prisms, pyramids, rhombohedra), or the ratio of the crystalline axes, and is connected with the optical and many other properties of crystals. Since the establishment of this law the description of definite compounds in a solid state is accompanied by a description (measurement) of its crystals, which forms an invariable, definite, and measurable character. The most important epochs in the further history of this question were made by the following discoveries :-Klaproth, Vauquelin, and others showed that aragonite has the same composition as calc spar, whilst the former belongs to the rhornbic and the latter to the hexagonal system. Haiiy at first considered that the composition, and after that the arrangement, of the atoms in the molecules was different. This is dimorphism (see Chapter XIV., Note 46). Beudant, Frankenheim, Laurent, and others found that the forms of the two nitres, KNO3 and NaNO3, exactly correspond with the forms of aragonite and calc spar; that they are able, moreover, to pass from one form into another; and that the difference of the forms is accompanied by a small alteration of the angles, for the angle of the prisms of potassium nitrate and aragonite is 119°, and of sodium nitrate and calc spar, 120°; and therefore dimorphism, or the
employed for discovering the analogy of elements and of their compounds; and as crystals are measurable, and the capacity to form
crystallisation of one substance in different forms, does not necessarily imply a great difference in the distribution of the molecules, although some difference clearly exists. The researches of Mitscherlich (1822) on the dimorphism of sulphur confirmed this conclusion, although it cannot yet be affirmed that in dimorphism the arrangement of the atoms remains unaltered, and that only the molecules are distributed differently. Leblanc, Berthier, Wollaston, and others already knew that many substances of different composition appear in the same forms, and crystallise together in one crystal. Gay-Lussac (1816) showed that crystals of potash alum continue to grow in a solution of ammonia alum. Beudant (1817) explained this phenomenon as the assimilation of a foreign substance by a substance having a great force of crystallisation, which he illustrated by many natural and artificial examples. But Mitscherlich, and afterwards Berzelius and Henry Rose and others, showed that such an assimilation only exists with a similarity or approximate similarity of the forms of the individual substances and with a certain degree of chemical analogy. Thus was established the idea of isomorphism as an analogy of forms by reason of a resemblance of atomic composition, and by it was explained the variability of the composition of a number of minerals as isomorphous mixtures. Thus all the garnets are expressed by the general formula : (RO); M.,O3(SiO.ls, where R=Ca, Mg, Fe, Mn, and M=Fe, Al, and where we may have either R and M separately, or their equivalent compounds, or their mixtures in all possible proportions.
But other facts, which render the correlation of form and composition still more complex, have accumulated side by side with a mass of data which may be accounted for by admitting the conceptions of isomorphism and dimorphism. Foremost among the former stand the phenomena of homeomorphism-that is, a nearness of forms with a difference of composition-and then the cases of polymorphism and hemimorphism--that is, a nearness of the fundamental forms or only of certain angles for substances which are near or analogous in their composition. Instances of homeomorphism are very numerous. Many of these, however, may be reduced to a resemblance of atomic composition, although they do not correspond to an isomorphism of the component elements; for example, Cds (greenockite) and AgI, CaCO3 (aragonite) and KNO3, CaCO3 (cale spar) and NaNO3, BaSO, (heavy spar), KMnO, (potassium permanganate), and KC104 (potassium perchlorate), Al,Oz (corundum) and FeTiOz (titanic iron ore), FeS., (marcasite, rhombic system) and FeSAs (arsenical pyrites), NiS and NiAs, &c. But besides these instances there are homeomorphous substances with an absolute dissimilarity of composition. Many such instances were pointed out by Dana. Cinnabar, Hgs, and susannite, PbS0,3PbCO; appear in very analogous crystalline forms; the acid potassium sulphate crystallises in the monoclinic system in crystals analogous to felspar, KAISI30; glauberite, Na2Ca(SOG)2, augite, RSiOz (R=Ca, Mg), sodium carbonate, Na.,CO3,10H,O, Glauber's salt, Na S0,,10H,O, and borax, Na,Br07,10H,O, not only belong to the same system (monoclinic), but exhibit an analogy of combinations and a nearness of corresponding angles. These and many other similar cases might appear to be perfectly arbitrary (especially as a nearness of angles and fundamental forms is a relative idea) were there not other cases where a resemblance of properties and a distinct relation in the variation of composition is connected with a resemblance of form. Thus, for example, alumina, Al,0z, and water, H.,0, are frequently found in many pyroxenes and amphiboles which only contain silica and magnesia (MgO, CaO, FeO, MnO). Scheerer and Hermann, and many others, endeavoured to explain such instances by polymetric isomorphism, stating that MgO may be replaced by 31,0 (for example, olivine and serpentine), SiO2 by A1,0(in the amphiboles, talcs), and so on. A certain number of the instances of this order are subject to doubt, because many of the natural minerals which served as the basis for the establishment of polymeric isomorphism in all probability no longer present their original composition, but one which has been altered under the influence of solutions which have come into contact