Page:EB1911 - Volume 06.djvu/86

 Polymorphism.—On the theory that crystal form and structure are the result of the equilibrium between the atoms and molecules composing the crystals, it is probable, a priori, that the same substance may possess different equilibrium configurations of sufficient stability, under favourable conditions, to form different crystal structures. Broadly this phenomenon is termed polymorphism; however, it is necessary to examine closely the diverse crystal modifications in order to determine whether they are really of different symmetry, or whether twinning has occasioned the apparent difference. In the article the nature and behaviour of twinned crystals receives full treatment; here it is sufficient to say that when the planes and axes of twinning are planes and axes of symmetry, a twin would exhibit higher symmetry (but remain in the same crystal system) than the primary crystal; and, also, if a crystal approximates in its axial constants to a higher system, mimetic twinning would increase the approximation, and the crystal would be pseudo-symmetric.

In general, polysymmetric and polymorphous modifications suffer transformation when submitted to variations in either temperature or pressure, or both. The criterion whether a pseudo-symmetric form is a true polymorph or not consists in the determination of the scalar properties (e.g. density, specific heat, &c.) of the original and the resulting modification, a change being in general recorded only when polymorphism exists. Change of temperature usually suffices to determine this, though in certain cases a variation in pressure is necessary; for instance, sodium magnesium uranyl acetate, NaMg(UO2)3(C2H3O2)9·9H2O shows no change in density unless the observations are conducted under a considerable pressure. Although many pseudo-symmetric twins are transformable into the simpler form, yet, in some cases, a true polymorph results, the change being indicated, as before, by alterations in scalar (as well as vector) properties.

While polysymmetry is solely conditioned by the manner in which the mimetic twin is built up from the single crystals, there being no change in the scalar properties, and the vector properties being calculable from the nature of the twinning, in the case of polymorphism entirely different structures present themselves, both scalar and vector properties being altered; and, in the present state of our knowledge, it is impossible to foretell the characters of a polymorphous modification. We may conclude that in polymorphs the substance occurs in different phases (or molecular aggregations), and the equilibrium between these phases follows definite laws, being dependent upon temperature and pressure, and amenable to thermodynamic treatment (cf. and ). The transformation of polymorphs presents certain analogies to the solidification of a liquid. Liquids may be cooled below their freezing-point without solidification, the metastable (after W. Ostwald) form so obtained being immediately solidified on the introduction of a particle of the solid modification; and supersaturated solutions behave in a similar manner. At the same time there may be conditions of temperature and pressure at which polymorphs may exist side by side.



The physical conditions under which polymorphous modifications are prepared control the form which the substance assumes. We have already seen that temperature and pressure exercise considerable influence in this direction. In the case of separation from solutions, either by crystallization or by precipitation by double decomposition, the temperature, the concentration of the solution, and the presence of other ions may modify the form obtained. In the case of sodium dihydrogen phosphate, NaH2PO4·H2O, a stable rhombic form is obtained from warm solutions, while a different, unstable, rhombic form is obtained from cold solutions. Calcium carbonate separates as hexagonal calcite from cold solutions (below 30°), and as rhombic aragonite from solutions at higher temperatures; lead and strontium carbonates, however, induce the separation of aragonite at lower temperatures. From supersaturated solutions the form unstable at the temperature of the experiment is, as a rule, separated, especially on the introduction of a crystal of the unstable form; and, in some cases, similar inoculation of the fused substance is attended by the same result. Different modifications may separate and exist side by side at one and the same time from a solution; e.g. telluric acid forms cubic and monoclinic crystals from a hot nitric acid solution, and ammonium fluosilicate gives cubic and hexagonal forms from aqueous solutions between 6° and 13°.

A comparison of the transformation of polymorphs leads to a twofold classification: (1) polymorphs directly convertible in a reversible manner—termed “enantiotropic” by O. Lehmann and (2) polymorphs in which the transformation proceeds in one direction only—termed “monotropic.” In the first class