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PRINCIPLES OF CHEMISTRY

CHAPTER XV

THE GROUPING OF THE ELEMENTS AND THE PERIODIC LAW

It is seen from the examples given in the preceding chapters that the suin of the data concerning the chemical transformations proper to the elements (for instance, with respect to the formation of acids, salts, and other compounds having definite properties) is insufficient for accurately determining the relationship of the elements, inasmuch as this may be many-sided. Thus, lithium and barium are in some respects analogous to sodium and potassium, and in others to magnesium and calcium. It is evident, therefore, that for a complete judgment it is necessary to have, not only qualitative, but also quantitative, exact and measurable, data. When a property can be measured it ceases to be vague, and becomes quantitative instead of merely qualitative..

Among these measurable properties of the elements, or of their corresponding compounds, are : (a) isomorphism, or the analogy of crystalline forms; and, connected with it, the power to form crystalline mixtures which are isomorphous ; (b) the relation of the volumes of analogous compounds of the elements ; (c) the composition of their saline compounds; and (d) the relation of the atomic weights of the elements. In this chapter we shall briefly consider these four aspects of the matter, which are exceedingly important for a natural and fruitful grouping of the elements, facilitating, not only a general acquaintance with them, but also their detailed study.

Historically the first, and an important and convincing, method for finding a relationship between the compounds of two different elements is by isomorphism. This conception was introduced into chemistry by Mitscherlich (in 1820), who demonstrated that the corresponding salts of arsenic acid, H,As0q, and phosphoric acid, H,PO,, crystallise VOL. II.

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with an equal quantity of water, show an exceedingly close resemblance in crystalline forin (as regards the angles of their faces and axes), and are able to crystallise together from solutions, forming crystals containing a mixture of the isomorphous compounds. Isomorphous subtances are those which, with an equal number of atoms in their molecules, present an analogy in their chemical reactions, a close resemblance in their properties, and a similar or very nearly similar crystalline form : they often contain certain elements in common, from which it is to be concluded that the remaining elements (as in the preceding example of As and P) are analogous to each other. And inasmuch as crystalline forms are capable of exact measurement, the external form, or the relation of the molecules which causes their grouping into a crystalline form, is evidently as great a help in judging of the internal forces acting between the atoms as a comparison of reactions, vapour densities, and other like relations. We have already seen examples of this in the preceding pages. It will be sufficient to call to mind that the compounds of the alkali metals with the halogens RX, in a crystalline form, all belong to the cubic system and crystallise in octahedra or cubes-for example, sodium chloride, potassium chloride, potassium iodide, rubidium chloride, &c. The nitrates of rubidium and cæsium appear in anhydrous crystals of the same form as potassium nitrate. The carbonates of the metals of the alkaline earths are isomorphous with calcium carbonate—that is, they either appear in forms like calc spar or in the rhombic system in crystals analogous to aragonite.Ibis Furthermore, sodium nitrate crystallises in rhombohedra, closely resembling the rhombohedra of calc spar (calcium carbonate), CaCO3, whilst potassium nitrate appears in the same form as aragonite, CaCO3, and the number of atoms in both kinds of salts is the same : they all contain one atom of a metal (K, Na, Ca), one atom of a non-metal (C, N), and three atoms of oxygen. The analogy of form evidently coincides with an analogy of atomic composition. But, as we have learnt from the previous description of these salts, there is not any close resemblance in their properties. It is evident that calcium carbonate approaches more nearly to magnesium carbonate than to sodium nitrate, although their crystalline forms are all equally alike. Isomorphous substances which are prefectly analogous to each other are not only characterised by a close resemblance of form (homeomorphism), but also by the faculty of entering into.analogous reactions, which is not the case with RNO, and RCO3. The most important and direct method of recognising perfect isomorphism—that is, the absolute analogy of two compounds - is given by that property of analogous compounds of separating from solutions in homogeneous crystals, containing the most varied proportions of the analogous substances which enter into their composition. These quantities do not seem to be in dependence on the molecular or atomic weights, and if they are governed by any laws they must be analogous to those which apply to indefinite chemical compounds. This will be clear from the following examples. Potassium chloride and potassium nitrate are not isomorphous with each other, and are in an atomic sense composed in a different manner. If these salts be mixed in a solution and the solution be evaporated, independent crystals of the two salts will separate, each in that crystalline form which is proper to it. The crystals will not contain a mixture of the two salts. But if we mix the solutions of two isomorphous salts together, then, under certain circumstances, crystals will be obtained which contain both these substances. However, this cannot be taken as an absolute rule, for if we take a solution saturated at a high temperature with a mixture of potassium and sodium chlorides, then on evaporation sodium chloride only will separate, and on cooling only potassium chloride.

1 For instance the analogy of the sulphates of K, Rh, and Cs (Chapter XIII., Note 1).

1 bis The crystalline forms of aragonite, strontianite, and witherite belong to the rhombic system; the angle of the prism of CaCO3 is 116° 10', of SrCO; 117° 19', and of BaC0, 118° 30'. On the other hand the crystalline forms of calc spar, magnesite, and calamine, which resemble each other quite as closely, belong to the rhombohedral system, with the angle of the rhombohedra for CaCO3 105° 8', MgCO; 107° 10', and ZnCO3 107 40'. From this comparison it is at once evident that zinc is more closely allied to magnesium than magnesium to calcium.

2 Solutions furnish the commonest examples of indefinite chemical compounds. But the isomorphous mixtures which are so cominon among the crystalline compounds of silica forming the crust of the earth, as well as alloys, which are so important in the application of metals to the arts, are also instances of indefinite compounds. And if in Chapter I., and in many other portions of this work, it has been necessary to admit the presence of definite compounds (in a state of dissociation) in solutions, the same applies with even greater force to isomorphous mixtures and alloys. For this reason in many places in this work I refer to facts which compel us to recognise the existence of definite chemical compounds in all isomorphous mixtures and alloys. This view of mine (which dates from the sixties) upon isomorphous mixtures finds a particularly clear confirmation in B. Roozeboom's researches (1892) upon the solubility and crystallising capacity of mixtures of the chlorates of potassium and thallium, KC10, and TIC103. He showed that when a solution contains different amounts of these salts, it deposits crystals containing either an excess of the first salt, from 98 p.c. to 100 p.c., or an excess of the second salt, from 63.7 to 100 p.c.; that is, in the crystalline form, either the first salt saturates the second or the second the first, just as in the solution of ether in water (Chapter I.); moreover, the solubility of the mixtures containing 36:3 and 98 p.c. KC103 is similar, just as the vapour tension of a saturated solution of water in ether is equal to that of a saturated solution of ether in water (Chapter I., Note 47). But just as there are solutions miscible in all proportions, so also certain isomorphous bodies can be present in crystals in all possible proportions of their component parts. Van 't Hoff calls such systems solid solutions. These views were subsequently elaborated by Nernst (1892), and Witt (1891) applied them in explaining the phenomena observed in the coloration of tissues.

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