Page:EB1911 - Volume 07.djvu/612

Rh As already mentioned, the optical properties of crystals vary considerably with the temperature. Such characters as specific heat and melting-point, which do not vary with the direction, are the same in crystals as in amorphous substances.

(d&#8202;) Magnetic and Electrical Properties.

Crystals, like other bodies, are either paramagnetic or diamagnetic, i.e. they are either attracted or repelled by the pole of a magnet. In crystals other than those belonging to the cubic system, however, the relative strength of the induced magnetization is different in different directions within the mass. A sphere cut from a tetragonal or hexagonal (uniaxial) crystal will if freely suspended in a magnetic field (between the poles of a strong electro-magnet) take up a position such that the principal axis of the crystal is either parallel or perpendicular to the lines of force, or to a line joining the two poles of the magnet. Which of these two directions is taken by the axis depends on whether the crystal is paramagnetic or diamagnetic, and on whether the principal axis is the direction of maximum or minimum magnetization. The surface expressing the magnetic character in different directions is in uniaxial crystals a spheroid; in cubic crystals it is a sphere. In orthorhombic, monoclinic and anorthic crystals there are three principal axes of magnetic induction, and the surface is an ellipsoid, which is related to the symmetry of the crystal in the same way as the ellipsoids expressing the thermal and optical properties.

Similarly, the dielectric constants of a non-conducting crystal may be expressed by a sphere, spheroid or ellipsoid. A sphere cut from a crystal will when suspended in an electro-magnetic field set itself so that the axis of maximum induction is parallel to the lines of force.

The electrical conductivity of crystals also varies with the direction, and bears the same relation to the symmetry as the thermal conductivity. In a rhombohedral crystal of haematite the electrical conductivity along the principal axis is only half as great as in directions perpendicular to this axis; whilst in a crystal of bismuth, which is also rhombohedral, the conductivities along and perpendicular to the axis are as 1.6:1.

Conducting crystals are thermo-electric: when placed against another conducting substance and the contact heated there will be a flow of electricity from one body to the other if the circuit be closed. The thermo-electric force depends not only on the nature of the substance, but also on the direction within the crystal, and may in general be expressed by an ellipsoid. A remarkable case is, however, presented by minerals of the pyrites group: some crystals of pyrites are more strongly thermo-electrically positive than antimony, and others more negative than bismuth, so that the two when placed together give a stronger thermo-electric couple than do antimony and bismuth. In the thermo-electrically positive crystals of pyrites the faces of the pentagonal dodecahedron are striated parallel to the cubic edges, whilst in the rarer negative crystals the faces are striated perpendicular to these edges. Sometimes both sets of striae are present on the same face, and the corresponding areas are then thermo-electrically positive and negative.

The most interesting relation between the symmetry of crystals and their electrical properties is that presented by the pyro-electrical phenomena of certain crystals. This is a phenomenon which may be readily observed, and one which often aids in the determination of the symmetry of crystals. It is exhibited by crystals in which there is no centre of symmetry, and the axes of symmetry are uniterminal or polar in character, being associated with different faces on the crystal at their two ends. When a non-conducting crystal possessing this hemimorphic type of symmetry is subjected to changes of temperature a charge of positive electricity will be developed on the faces in the region of one end of the uniterminal axis, whilst the faces at the opposite end will be negatively charged. With rising temperature the pole which becomes positively charged is called the “analogous pole,” and that negatively charged the “antilogous pole”: with falling temperature the charges are reversed. The phenomenon was first observed in crystals of tourmaline, the principal axis of which is a uniterminal triad axis of symmetry. In crystals of quartz there are three uniterminal dyad axes of symmetry perpendicular to the principal triad axis (which is here similar at its two ends): the dyad axes emerge at the edges of the hexagonal prism, alternate edges of which become positively and negatively charged on change of temperature. In boracite there are four uniterminal triad axes, and the faces of the two tetrahedra perpendicular to them will bear opposite charges. Other examples of pyro-electric crystals are the orthorhombic mineral hemimorphite (called also, for this reason, “electric calamine”) and the monoclinic tartaric acid and cane-sugar, each of which possesses a uniterminal dyad axis of symmetry. In some exceptional cases, e.g. axinite, prehnite, &c., there is no apparent relation between the distribution of the pyro-electric charges and the symmetry of the crystals.

The distribution of the electric charges may be made visible by the following simple method, which may be applied even with minute crystals observed under the microscope. A finely powdered mixture of red-lead and sulphur is dusted through a sieve over the cooling crystal. In passing through the sieve the particles of red-lead and sulphur become electrified by mutual friction, the former positively and the latter negatively. The red-lead is therefore attracted to the negatively charged parts of the crystal and the sulphur to those positively charged, and the distribution of the charges over the whole crystal becomes mapped out in the two colours red and yellow.

Since, when a crystal changes in temperature, it also expands or contracts, a similar distribution of “piezo-electric” (from, to press) charges are developed when a crystal is subjected to changes of pressure in the direction of a uniterminal axis of symmetry. Thus increasing pressure along the principal axis of a tourmaline crystal produces the same electric charges as decreasing temperature.

'''III. RELATIONS BETWEEN CRYSTALLINE FORM AND CHEMICAL COMPOSITION.'''

That the general and physical characters of a chemical substance are profoundly modified by crystalline structure is strikingly illustrated by the two crystalline modifications of the element carbon—namely, diamond and graphite. The former crystallizes in the cubic system, possesses four directions of perfect cleavage, is extremely hard and transparent, is a non-conductor of heat and electricity, and has a specific gravity of 3.5; whilst graphite crystallizes in the hexagonal system, cleaves in a single direction, is very soft and opaque, is a good conductor of heat and electricity, and has a specific gravity of 2.2. Such substances, which are identical in chemical composition, but different in crystalline form and consequently in their physical properties, are said to be “dimorphous.” Numerous examples of dimorphous substances are known; for instance, calcium carbonate occurs in nature either as calcite or as aragonite, the former being rhombohedral and the latter orthorhombic; mercuric iodide crystallizes from solution as red tetragonal crystals, and by sublimation as yellow orthorhombic crystals. Some substances crystallize in three different modifications, and these are said to be “trimorphous”; for example, titanium dioxide is met with as the minerals rutile, anatase and brookite (q.v.). In general, or in cases where more than three crystalline modifications are known (e.g. in sulphur no less than six have been described), the term “polymorphism” is applied.

On the other hand, substances which are chemically quite distinct may exhibit similarity of crystalline form. For example, the minerals iodyrite (AgI), greenockite (CdS), and zincite (ZnO) are practically identical in crystalline form; calcite (CaCO3) and sodium nitrate (NaNO3); celestite (SrSO)4 and marcasite (FeS2); epidote and azurite; and many others, some of which are no doubt only accidental coincidences. Such substances are said to be “homoeomorphous” (Gr., like, and  , form).

Similarity of crystalline form in substances which are chemically related is frequently met with and is a relation of much