Solid binary oxides, structure-bonding

Classification of Structure-Bonding in Solid Binary Oxides... 

Kubaschewski (1972) collected and compared the enthalpies of formation of complex oxides from binary oxides. He did not offer any systematic correlation of these enthalpies with structural properties. Hoppe (1966,1970a, b, 1975) developed the MAPLE concept (Madelung part of lattice energy) as a tool to guide the structural interpretation of bonding in complex oxides and halides. It requires as input parameters the unit cell of a compound and positions of all atoms, and it treats the crystal as an ionic array of point charges. If crystal structure determinations have been properly done, MAPLE calculations for a complex compound are within 2% (sometimes larger, sometimes smaller) of the MAPLE values of the binary (parent) compounds. Therefore, purely ionic-model calculations are not suflftciently sensitive to correlate quantitatively with the relatively small enthalpies of solid-state complexation. 

Soluble heptapnicanortricyclane anions [Pny] (Fig. 3a) and trishomocubane-shaped (ufosane-like) anions [Pnn] (Fig. 3d) are very common and known as in the binary solids for Pn = P, As, Sb (Table 2). Oxidative coupling of these monomers leads to the dimers [Pny-Pny]" and [Pnn-Pnn]" for Pn = P and As (Fig. 3b, e), which - as observed for the tetrel element clusters - have an external homoatomic bond, but in this case the structures of the monomeric units are fully retained upon dimerization. A trimeric oxidative coupling product of [Py] is the... 

We comment elsewhere on the inadequacy of current bonding theory to account for the complexity of some binary systems in which solid phases appear with unexpected formulae and/or properties-for example, the oxides of caesium and the nitrides of calcium. Certain transition metals, notably Ti, V, Nb, Mo, and W, have a suprisingly complex oxide chemistry, and although it may be difficult to appreciate all the features of their structures from diagrams, these compounds are sufficiently important to justify mention here. 

Abstract Refractory oxides encompass a broad range of unary, binary, and ternary ceramic compounds that can be used in structural, insulating, and other applications. The chemical bonds that provide cohesive energy to the crystalline solids also influence properties such as thermal expansion coefficient, thermal conductivity, elastic modulus, and heat capacity. This chapter provides a historical perspective on the use of refractory oxide materials, reviews applications for refractory oxides, overviews fundamental structure-property relations, describes typical processing routes, and summarizes the properties of these materials. 

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