[Atomic volume, packing density of the atoms, and chemical bonds in nonmetallic elements].
The atomic volume of crystalline elements is largely determined by the packing density of atoms in the respective modification. The determination of packing density is improved by assuming that the atomic distances depend on bond valences according to Pauling's equation. With the additional assumption of equal valence in different modifications, the experimental atomic volume of an element in any given structure is reduced to its volume in close-packed structures, e.g. f.c.c. The ratio of this reduced atomic volume and the experimental atomic volume is a measure of packing density. Reduced atomic volumes of C, Si, Ge, P, As, S and Se, as calculated from different modifications, correspond in most cases to within less than +/-1% for each element, even if calculated from extremely different structures like diamond and buckminsterfullerene in the case of carbon, or from numerous modifications of sulfur with annular molecules of different sizes. Exceptions (graphite, white phosphorus, tin and selenium) indicate deviating valences.
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Institut für Anorganische und Analytische Chemie der J. W. Goethe-Universität, Max von Laue-Strasse 7, D-60438 Frankfurt am Main, Germany. troemel@chemie.uni-frankfurt.de