Page:EB1911 - Volume 06.djvu/86

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PHYSICAL]
73
CHEMISTRY

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 Crystallography 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.

For example, boracite forms pseudo-cubic crystals which become truly cubic at 265°, with a distinct change in density; leucite behaves similarly at about 560°. Again, the pyroxenes, RSiO3 (R = Fe, Mg, Mn, &c.), assume the forms (1) monoclinic, sometimes twinned so as to become pseudo-rhombic; (2) rhombic, resulting from the pseudo-rhombic structure of (1) becoming ultramicroscopic; and (3) triclinic, distinctly different from (1) and (2); (1) and (2) are polysymmetric modifications, while (3) and the pair (1) and (2) are polymorphs.

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. Chemical Action and Energetics). 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.

EB1911 Chemistry - Fig. 6.jpg

The above may be illustrated by considering the equilibrium between rhombic and monoclinic sulphur. The former, which is deposited from solutions, is transformed into monoclinic sulphur at about 96°, but with great care it is possible to overheat it and even to fuse it (at 113.5°) without effecting the transformation. Monoclinic sulphur, obtained by crystallizing fused sulphur, melts at 119.5°, and admits of undercooling even to ordinary temperatures, but contact with a fragment of the rhombic modification spontaneously brings about the transformation. From Reicher’s determinations, the exact transition point is 95.6°; it rises with increasing pressure about 0.05° for one atmosphere; the density of the rhombic form is greater than that of the monoclinic. The equilibria of these modifications may be readily represented on a pressure-temperature diagram. If OT, OP (fig. 6), be the axes of temperature and pressure, and A corresponds to the transition point (95.6°) of rhombic sulphur, we may follow out the line AB which shows the elevation of the transition point with increasing pressure. The overheating curve of rhombic sulphur extends along the curve AC, where C is the melting-point of monoclinic sulphur. The line BC, representing the equilibrium between monoclinic and liquid sulphur, is thermodynamically calculable; the point B is found to correspond to 131° and 400 atmospheres. From B the curve of equilibrium (BD) between rhombic and liquid sulphur proceeds; and from C (along CE) the curve of equilibrium between liquid sulphur and sulphur vapour. Of especial interest is the curve BD: along this line liquid and rhombic sulphur are in equilibrium, which means that at above 131° and 400 atmospheres the rhombic (and not the monoclinic) variety would separate from liquid sulphur.

Mercuric iodide also exhibits dimorphism. When precipitated from solutions it forms red tetragonal crystals, which, on careful heating, give a yellow rhombic form, also obtained by crystallization from the fused substance, or by sublimation. The transition point is 126.3° (W. Schwarz, Zeit. f. Kryst. 25, p. 613), but both modifications may exist in metastable forms at higher and lower temperatures respectively; the rhombic form may be cooled down to ordinary temperature without changing, the transformation, however, being readily induced by a trace of the red modification, or by friction. The density and specific heat of the tetragonal form are greater than those of the yellow.

Hexachlorethane is trimorphous, forming rhombic, triclinic and cubic crystals; the successive changes occur at about 44° and 71°, and are attended by a decrease in density.

Tetramorphism is exhibited by ammonium nitrate. According to O. Lehmann it melts at 168° (or at a slightly lower temperature in its water of crystallization) and on cooling forms optically isotropic crystals; at 125.6° the mass becomes doubly refracting, and from a solution rhombohedral (optically uniaxial) crystals are deposited; by further cooling acicular rhombic crystals are produced at 82.8°, and at 32.4° other rhombic forms are obtained, identical with the product obtained by crystallizing at ordinary temperatures. The reverse series of transformations occurs when this final modification is heated. M. Bellati and R. Romanese (Zeit. f. Kryst. 14, p. 78) determined the densities and specific heats of these modifications. The first and third transformations (reckoned in order with increasing temperature of the transition point) are attended by an increase in volume, the second with a contraction; the solubility follows the same direction, increasing up to 82.8°, then diminishing up to 125.6°, and then increasing from this temperature upwards.

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