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PHYSICAL]
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CHEMISTRY

manner. The ordinary structural formula of potassium sulphate is EB1911 Chemistry - potassium sulphate.jpg If the crystal structure be regarded as composed of three interpenetrating point systems, one consisting of sulphur atoms, the second of four times as many oxygen atoms, and the third of twice as many potassium atoms, the systems being so arranged that the sulphur system is always centrally situated with respect to the other two, and the potassium system so that it would affect the vertical axis, then it is obvious that the replacement of potassium by an element of greater atomic weight would specially increase the length of ω (corresponding to the vertical axis), and cause a smaller increase in the horizontal parameters χ and ψ; moreover, the increments would advance with the atomic weight of the replacing metal. If, on the other hand, the sulphur system be replaced by a corresponding selenium system, an element of higher atomic weight, it would be expected that a slight increase would be observed in the vertical parameter, and a greater increase recorded equally in the horizontal parameters.

Muthmann (Zeit. f. Kryst., 1894), in his researches on the tetragonal potassium and ammonium dihydrogen phosphates and arsenates, found that the replacement of potassium by ammonium was attended by an increase of about six units in the molecular volume, and of phosphorus by arsenic by about 4.6 units. In the topic parameters the following changes were recorded: replacement of potassium by ammonium was attended by a considerable increase in ω, χ and ψ being equally, but only slightly, increased; replacement of phosphorus by arsenic was attended by a considerable increase, equally in χ and ψ, while ω suffered a smaller, but not inconsiderable, increase. It is thus seen that the ordinary plane representation of the structure of compounds possesses a higher significance than could have been suggested prior to crystallographical researches.

EB1911 Chemistry - Figs. 7-8.jpg

Identity, or approximate identity, of crystal form is not in itself sufficient to establish true isomorphism. If a substance deposits itself on the faces of a crystal of another substance of similar crystal form, the substances are probably isomorphous. Such parallel overgrowths, termed episomorphs, are very common among the potassium and sodium felspars; and K. von Hauer has investigated a number of cases in which salts exhibiting episomorphism have different colours, thereby clearly demonstrating this property of isomorphism. For example, episomorphs of white potash alum and violet chrome alum, of white magnesium sulphate and green nickel sulphate, and of many other pairs of salts, have been obtained. More useful is the property of isomorphous substances of forming mixed crystals, which are strictly isomorphous with their constituents, for all variations in composition. In such crystals each component plays its own part in determining the physical properties; in other words, any physical constant of a mixed crystal can be calculated as additively composed of the constants of the two components.


Fig. 7 represents the specific volumes of mixtures of ammonium and potassium sulphates; the ordinates representing specific volumes, and the abscissae the percentage composition of the mixture. Fig. 8 shows the variation of refractive index of mixed crystals of potash alum and thallium alum with variation in composition.

In these two instances the component crystals are miscible in all proportions; but this is by no means always the case. It may happen that the crystals do not form double salts, and are only miscible in certain proportions. Two cases then arise: (1) the properties may be expressed as linear functions of the composition, the terminal values being identical with those obtained for the individual components, and there being a break in the curve corresponding to the absence of mixed crystals; or (2) similar to (1) except that different values must be assigned to the terminal values in order to preserve collinearity. Fig. 9 illustrates the first case: the ordinates represent specific volumes, and the abscissae denote the composition of isomorphous mixtures of ammonium and potassium dihydrogen phosphates, which mutually take one another up to the extent of 20% to form homogeneous crystals. The second case is illustrated in fig. 10. Magnesium sulphate (orthorhombic) takes up ferrous sulphate (monoclinic) to the extent of 19%, forming isomorphous orthorhombic crystals; ferrous sulphate, on the other hand, takes up magnesium sulphate to the extent of 54% to form monoclinic crystals. By plotting the specific volumes of these mixed crystals as ordinates, it is found that they fall on two lines, the upper corresponding to the orthorhombic crystals, the lower to the monoclinic. From this we may conclude that these salts are isodimorphous: the upper line represents isomorphous crystals of stable orthorhombic magnesium sulphate and unstable orthorhombic ferrous sulphate, the lower line isomorphous crystals of stable monoclinic ferrous sulphate and unstable monoclinic magnesium sulphate.

EB1911 Chemistry - Fig. 9.jpg


Fig. 10.

An important distinction separates true mixed crystals and crystallized double salts, for in the latter the properties are not linear functions of the properties of the components; generally there is a contraction in volume, while the refractive indices and other physical properties do not, in general, obey the additive law.

Isomorphism is most clearly discerned between elements of analogous chemical properties; and from the wide generality of such observations attempts have been made to form a classification of elements based on isomorphous replacements. The following table shows where isomorphism may be generally expected. The elements are arranged in eleven series, and the series are subdivided (as indicated by semicolons) into groups; these groups exhibit partial isomorphism with the other groups of the same series (see W. Nernst, Theoretical Chemistry).

Series  1. Cl, Br, I, F; Mn (in permanganates).
 2. S, Se; Te (in tellurides); Cr, Mn, Te (in the acids H2RO4); As, Sb (in the glances MR2).
 3. As, Sb, Bi; Te (as an element); P, Vd (in salts); N, P (in organic bases).
 4. K, Na, Cs, Rb, Li; Tl, Ag.
 5. Ca, Ba, Sr, Pb; Fe, Zn, Mn, Mg; Ni, Co, Cu; Ce, La, Di, Er, Y, Ca; Cu, Hg, Pb; Cd, Be, In, Zn; Tl, Pb.
 6. Al, Fe, Cr, Mn; Ce, U (in sesquioxides).
 7. Cu, Ag (when monovalent); Au.
 8. Pt, Ir, Pd, Rh, Ru, Os; Au, Fe, Ni; Sn, Te.
 9. C, Si, Ti, Zr, Th, Sn; Fe, Ti.
10. Ta, Cb (Nb).
11. Mo, W, Cr.

For a detailed comparison of the isomorphous relations of the elements the reader is referred to P. von Groth, Chemical Crystallography. Reference may also be made to Ida Freund, The Study of Chemical Composition; and to the Annual Reports of the Chemical Society for 1908, p. 258.

Bibliography.—History: F. Hoefer, Histoire de la chimie (2nd ed., 1866–1869); Hermann Kopp, Geschichte der Chemie (1869), Entwickelung der Chemie in d. neueren Zeit (1871–1874); E. von Meyer, Geschichte der Chemie (3rd ed., 1905, Eng. trans.); A. Ladenburg, Entwickelungsgeschichte der Chemie (4th ed., 1907); A. Stange, Die Zeitalter der Chemie (1908). Reference may also be made to M. M. Pattison Muir, History of Chemical Theories and Laws (1907); Ida Freund, Study of Chemical Composition (1904); T. E. Thorpe, Essays in Historical Chemistry (2nd ed., 1902). See also the article Alchemy.

Principles and Physical.—W. Ostwald, Principles of Inorganic Chemistry (3rd Eng. ed., 1908), Outlines of General Chemistry, Lehrbuch der allgemeinen Chemie; W. Nernst, Theoretische Chemie (4th ed., 1907, Eng. trans.); J. H. van’t Hoff, Lectures on Theoretical and Physical Chemistry; J. Walker, Introduction to Physical Chemistry (4th ed., 1907); H. C. Jones, Outlines of Physical Chemistry (1903); D. Mendeléeff, Principles of Chemistry (3rd ed., 1905).

Inorganic.—Roscoe and Schorlemmer, Inorganic Chemistry (3rd ed., Non-metals, 1905; Metals, 1907); R. Abegg, Handbuch der anorganischen Chemie; Gmelin-Kraut, Handbuch der anorganischen Chemie; O. Dammer, Handbuch der anorganischen Chemie; H. Moissan, Chimie minérale.

Organic.—F. Beilstein, Handbuch der organischen Chemie; M. M. Richter, Lexikon der Kohlenstoffverbindungen (these are primarily works of reference); V. Meyer and P. H. Jacobson, Lehrbuch der organischen Chemie; Richter-Anschutz, Organische Chemie (11th ed.,