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AND CHEMICAL COMPOSITION

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Originally appearing in Volume V07, Page 591 of the 1911 Encyclopedia Britannica.
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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 sub-stances 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 " tri morphous "; 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. 6/.Lows, like, and µop4, form). Similarity of crystalline form in substances which are chemically related is frequently met with and is a relation of much importance: such substances are described as being " isomorphous." Amongst minerals there are many examples of isomorphous groups, e.g. the rhombohedral carbonates, garnet (q.v.), plagioclase (q.v.); and amongst crystals of artificially prepared salts isomorphism is equally common, e.g. the sulphates and selenates of potassium, rubidium and caesium. The rhombohedral carbonates have the general formula R"CO3, where R" represents calcium, magnesium, iron, manganese, zinc, cobalt or lead, and the different minerals (calcite, ankerite, magnesite, chalybite, rhodochrosite and calamine (q.v.)) of the group are not only similar in crystalline form, cleavage, optical and other characters, but the angles between corresponding faces do not differ by more than 1° or 2°. Further, equivalent amounts of the different chemical elements represented by R" are mutually replaceable, and two or more of these elements may be present together in the same crystal, which is then spoken of as a " mixed crystal " or isomorphous mixture. In another isomorphous series of carbonates with the same general formula R" CO3, where R" represents calcium, strontium, barium, lead or zinc, the. crystals are orthorhombic in form, and are thus dimorphous with those of the previous group (e.g. calcite and aragonite, the other members being only represented by isomorphous replacements). Such a relation is known as " isodimorphism." An even better example of this is presented by the arsenic and antimony trioxides, each of which occurs as two distinct minerals: As2Os, Arsenolite (cubic) ; Claudetite (monoclinic). Sb20,, Senarmontite (cubic) ; Valentinite (orthorhombic). Claudetite and valentinite though crystallizing in different systems have the same cleavages and very nearly the same angles, and are strictly isomorphous. Substances which form isodimorphous groups also frequently crystallize as double salts. For instance, amongst the carbonates quoted above are the minerals dolomite (CaMg(COs)2) and barytocalcite (CaBa(CO3)2). Crystals of barytocalcite (q.v.) are monoclinic; and those of dolomite (q.v.), though closely related to calcite in angles and cleavage, possess a different degree of symmetry, and the specific gravity is not such as would result by a simple isomorphous mixture of the two carbonates. A similar case is presented by artificial crystals of silver nitrate, and potassium nitrate. Somewhat analogous to double salts are the molecular compounds formed by the introduction of " water of crystallization," " alcohol of crystallization," &c. Thus sodium sulphate may crystallize alone or with either seven or ten molecules of water, giving rise to three crystallographically distinct substances. A relation of another kind is the alteration in crystalline form resulting from the replacement in the chemical molecule of one or more atoms by atoms or radicles of a different kind. This is known as a " morphotropic " relation (Gr. ,uop¢ii, form, Tp67ros, habit). Thus when some of the hydrogen atoms of benzene are replaced by (OH) and (NO2) groups the orthorhombic system of crystallization remains the same as before, and the crystallographic axis a is not much affected, but the axis c varies considerably: Benzene, C6H6 Resorcin, C6H,(OH)2 Picric acid ,C6H2(OH)(NO2)s A striking example of morphotropy is shown by the humite (q.v.) group of. minerals: successive additions of the group Mg2SiO4 to the molecule produce successive increases in the length of the vertical crystallographic axis. In some instances the replacement of one atom by another produces little or no influence on the crystalline form; this ,.happens in complex molecules of high molecular weight, the " mass effect " of which has a controlling influence on the isomorphism. An example of this is seen in the replacement of sodium or potassium by lead in the alunite (q.v.) group of minerals, or again in such a complex mineral as tourmaline, which, though varying widely in chemical composition, exhibits no variation 'in crystalline form. For the purpose of comparing the crystalline forms of isomorphous and morphotropic substances it is usual to quote the angles or the axial ratios of the crystal, as in the table of benzene derivatives quoted above. A more accurate comparison is, how-ever, given by the " topic axes," which are calculated from the axial ratios and the molecular volume; they express the relative distances apart of the crystal molecules in the axial directions. The two isomerides of substances, such as tartaric acid, which in solution rotate the plane of polarized light either to the right or to the left, crystallize in related but enantiomorphous forms. For geometrical crystallography, dealing exclusively with the external form of crystals, reference may be made to N. Story-Maskelyne, Crystallography, a Treatise on the Morphology of Crystals (Oxford, 1895) and W. J. Lewis, A Treatise on Crystallography (Cambridge, 1899). Theories of crystal structure are discussed by L. Sohncke, Entwickelung einer Theorie der Krystallstruktur (Leipzig, 1879) ; A. Schoenflies, Krystallsysteme and Krystallstructur (Leipzig, 1891) ; and H. Hilton, Mathematical Crystallography and the Theory of Groups of Movements (Oxford, 1903). The physical properties of crystals are treated by T. Liebisch, Physikalische Krystallographie (Leipzig, 1891), and in a more elementary form in his Grundriss der physikalischen Krystallographie (Leipzig, 1896) ; E. Mallard, Traite de cristallographie, Cristallographie physique (Paris, 1884) ; C. Soret, Elements de cristallographie physique (Geneva and Paris, 1893). For an account of the relations between crystalline form and chemical composition, see A. Arzruni, Physikalische Chemie der Krystalle (Braunschweig, 1893) ; A. Fock, An Introduction to Chemical Crystallography, translated by W. J. Pope (Oxford, 1895) ; P. Groth, An Introduction to Chemical Crystallography, translated by H. Marshall (London, 1906) ; A. E. H. Tutton, Crystalline Structure and Chemical Constitution, 1910. Descriptive works giving the crystallographic constants of different substances are C. F. Rammelsberg, Handbuch der krystallographisch-physikalischen Chemie (Leipzig, 1881-1882) ; P. Groth, Chemische Krystallographie (Leipzig, 1906) ; and of minerals the treatises of J. D. Dana and C. Hintze. (L. J. S.)
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