Fig. 62.—Diagram illustrating Progressive Rotation of Optical Ellipsoid in Monoclinic Isomorphous Series.
In the rubidium salt the ellipsoid has rotated over to the left, as indicated by the dotted ellipse, for a few degrees, the number of which varies slightly for the different groups of double salts; while in the cæsium salt it has swung over much more still, to the place marked by the ellipse drawn in broken line. In both this and the last illustration it will be remarked that the optical change is greater between the rubidium and cæsium salts than it is between the potassium and rubidium salts, the reason being that the optical properties are usually functions (of the atomic weight of the interchangeable elements) which are of an order higher than the first corresponding to simple proportionality.
These three ocular illustrations may serve to render this interesting law of progression, according to the atomic weight of the interchangeable elements which give rise to the isomorphous series, clearer to the mind, by placing before it concrete instances of the operation of the law.
The generalisation itself may be very concisely expressed in the statement that:
The whole of the properties, morphological and physical, of the crystals of an isomorphous series of salts are functions of the atomic weights of the interchangeable chemical elements of the same family group which give rise to the series.
The fact that this law extends to the structural dimensions, equally with all other morphological properties, as stated under (3) at the beginning of this chapter, is of especial interest. For it has actually been found possible to determine the relations of the dimensions of the unit parallelepipeda of the space-lattices of the various salts, that is, the separation of the molecular points of the space-lattice in the directions of the three crystal axes, for the various salts of the isomorphous series. This is achieved by combining in suitable formulæ the volume of the unit cell of the space-lattice with the relative lengths of the three crystal axes, a, b, c.
The axial ratios a : b : c are calculated from the measurements of the crystal angles, as explained in Chapter VI., page [68], and the volume is the physical constant long known as “molecular volume,” but now for the first time understood as regards its meaning in the case of solid substances. It is the quotient of the chemical constant molecular weight (the sum of the atomic weights, taking into account the number of atoms of each element present) by the specific gravity of the substance, here the solid crystal. Very great care has been taken to obtain absolutely accurate determinations of the specific gravities of the salts, as much depends on this now very valuable physical constant, and all the values obtained were reduced to the constant reference temperature of 20°, as the density notoriously alters rapidly with change of temperature.
We have thus arrived at morphological constants of very considerable importance, which are best termed “Molecular Distance Ratios,” as they express the relative distances apart in the three directions of space of the centres of gravity or other representative points of contiguous chemical molecules. They are dependent on three experimental determinations, atomic weight, specific gravity, and crystal angles, all of which have now been brought to the highest pitch of refinement and accuracy; hence the molecular distance ratios are particularly trustworthy constants. If it were only known how much is matter and how much is space in the molecular parallelepipedal cell, we should actually have in these constants a relative measure of the sizes of the molecules. They do give us, however, the relative directional dimensions of the molecular unit parallelepipedal cells of the space-lattices of the various members of the isomorphous series, just as the molecular volumes give us the relative volumes of these cells. For in an isomorphous series we are absolutely sure that the plan on which the space-lattice is constructed, its style of architecture, is identical for all the members of the isomorphous series. Hence, the molecular distance ratios are in these cases absolutely valid and strictly comparable. The ratios are generally expressed by the Greek letters χ : ψ : ω.
On comparing the molecular distance ratios for a potassium, a rubidium, and a cæsium salt of any of the series of sulphates, selenates, permanganates, perchlorates, double sulphates or double selenates investigated, we invariably find that the values of χ, ψ, and ω for the rubidium salt (rubidium having the intermediate atomic weight) lie between the analogous sets of three values for the potassium and cæsium salts respectively, in complete accordance with the law.