Cationic vacancies definition

For definiteness, the oxidation of copper to copper(l) oxide may be considered. Our picture of the process is that cation vacancies and positive holes formed at the Cu O/Oj interface by equation, 1.166 are transported to the Cu/CujO interface where they are destroyed by copper dissolving in the non-stoichiometric oxide. We require an expression for the rate of oxidation. 

Dowden (27) considers the active centers for carbonium ion formation to be associated with surface cation vacancies. A proton, derived from water contained in the catalyst, is attracted to the anions surrounding the vacancy. A hydrocarbon molecule is assumed to be held by polarization forces above this lattice defect and the proton will be distributed between the hydrocarbon and the anions, forming a carbonium ion of a definite lifetime. 

In this case, then, the chemical diffusion coefficient 5 is given by 5 = 2Dy Dsri /(Dy -h i srk)-Furthermore, the dissolved strontium ions can only diffuse via cation vacancies, and so, in the absence of association with vacancies, can be assumed to be small compared to Dy. Therefore, D csi 2Dsrj. The same result could be obtained by using the definition of the chemical diffusion coefficient from eq. (5-33) as well as eq. (5-38) and the condition of electrical neutrality. 

Since the ratio of number of anions to cations in a unit cell for the Fluorite structure is 1 to 2, the compound Zro.gsCao isOj 5 can be said to be non-stoichiometric. The possible defect types are anion vacancies or interstitial cations. X-ray diffraction studies have definitely confirmed that the former type of defect structure is dominant therefore, there exist oxygen vacancies up to 7.5 per cent. The concentration of oxygen vacancies must depend on Po., as is usual for the metal oxides. 

In compound crystals, balanced-defect reactions must conserve mass, charge neutrality, and the ratio of the regular lattice sites. In pure compounds, the point defects that form can be classified as either stoichiometric or nonstoichiometric. By definition, stoichiometric defects do not result in a change in chemistry of the crystal. Examples are Schottky (simultaneous formation of vacancies on the cation and anion sublattices) and Frenkel (vacancy-interstitial pair). 

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