Chemistry of Non-stoichiometric Compounds by Koji Kosuge

By Koji Kosuge

This unified presentation of the chemistry of non-stoichiometric compounds is the 1st monograph at the topic for 2 many years. in keeping with statistical thermodynamics and structural inorganic chemistry, with descriptions of contemporary examples and functions, this may be invaluable to either researchers in and undergraduates in good country chemistry and physics.

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The most obvious external characteristic of a crystal is that it has flat faces bounded by straight edges, but this property is not necessary 9 Real crystals often exhibit a variety of imperfections—for example, short-range or long-range disorder, dislocations, irregular surfaces, twinning, and other kinds of defects—but, for our present purposes, it is a good approximation to consider that in a specimen of a single crystal the order is perfect and three-dimensional. We discuss very briefly in Chapter 13 the way in which our discussion must be modified when some disorder is present—for example, when the order is only onedimensional, as in many fibers.

A one-carat diamond, which has approximately the volume of Fig. 3 An electron micrograph of a crystalline protein. An electron micrograph of a crystalline protein, fumarase, molecular weight about 200,000. The individual molecules, in white, are visible as approximately spherical structures at low resolution. Note that several choices of unit cell are possible. (Photograph courtesy of Dr. L. D. ‡ A typical crystal suitable for X-ray structure analysis, a few tenths of a millimeter in average dimension, contains 1012 to 1018 unit cells, each with identical contents that can diffract X rays in unison.

Since a crystal is built up of an extremely large number of regularly stacked cells, each of which has identical contents, the problem of determining the structure of a crystal is reduced to that of determining the spatial arrangement of the atoms within a single unit cell, or within the smaller asymmetric unit if (as is usual) the unit cell has some internal symmetry. If there is some static disorder in the structure, the arrangements of atoms in different unit cells may not be precisely identical, varying in an apparently random fashion.

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