Oxide surface/oxygen thermodynamic equilibrium

We cover each of these types of examples in separate chapters of this book, but there is a clear connection as well. In all of these examples, the main factor that maintains thermodynamic disequilibrium is the living biosphere. Without the biosphere, some abiotic photochemical reactions would proceed, as would reactions associated with volcanism. But without the continuous production of oxygen in photosynthesis, various oxidation processes (e.g., with reduced organic matter at the Earth s surface, reduced sulfur or iron compounds in rocks and sediments) would consume free O2 and move the atmosphere towards thermodynamic equilibrium. The present-day chemical functioning of the planet is thus intimately tied to the biosphere. 

On a freshly cleaved sample the surface composition is the same as the bulk composition (fig. 31 A). Because the surface energy of La is lower than that of Ni the surface becomes somewhat La enriched in thermodynamic equilibrium (fig. 31B). This segregation is enhanced by reaction with oxygen, and a La-oxide layer covers a Ni-rich layer (fig. 31C). The concentration profile of the decomposed surface layer is depicted schematically in fig. 3ID. 

To fully understand the formation of the N13S2 scale under certain gas conditions, a brief description needs to be given on the chemical aspects of the protective (chromium oxide) Ci 203/(nickel oxide) NiO scales that form at elevated temperatures. Under ideal oxidizing conditions, the alloy Waspaloy preferentially forms a protective oxide layer of NiO and Ci 203 The partial pressure of oxygen is such that these scales are thermodynamically stable and a condition of equilibrium is observed between the oxidizing atmosphere and the scale. Even if the scale surface is damaged or removed, the oxidizing condition of the atmosphere would preferentially reform the oxide scales. 

In some metal components it is possible to form oxides and carbides, and in others, especially those with a relatively wide solid solubility range, to partition the impurity between the solid and the liquid metal to provide an equilibrium distribution of impurities around the circuit. Typical examples of how thermodynamic affinities affect corrosion processes are seen in the way oxygen affects the corrosion behaviour of stainless steels in sodium and lithium environments. In sodium systems oxygen has a pronounced effect on corrosion behaviour whereas in liquid lithium it appears to have less of an effect compared with other impurities such as C and Nj. According to Casteels Li can also penetrate the surface of steels, react with interstitials to form low density compounds which then deform the surface by bulging. For further details see non-metal transfer. 

The mixed-potential model demonstrated the importance of electrode potential in flotation systems. The mixed potential or rest potential of an electrode provides information to determine the identity of the reactions that take place at the mineral surface and the rates of these processes. One approach is to compare the measured rest potential with equilibrium potential for various processes derived from thermodynamic data. Allison et al. (1971,1972) considered that a necessary condition for the electrochemical formation of dithiolate at the mineral surface is that the measmed mixed potential arising from the reduction of oxygen and the oxidation of this collector at the surface must be anodic to the equilibrium potential for the thio ion/dithiolate couple. They correlated the rest potential of a range of sulphide minerals in different thio-collector solutions with the products extracted from the surface as shown in Table 1.2 and 1.3. It can be seen from these Tables that only those minerals exhibiting rest potential in excess of the thio ion/disulphide couple formed dithiolate as a major reaction product. Those minerals which had a rest potential below this value formed the metal collector compoimds, except covellite on which dixanthogen was formed even though the measured rest potential was below the reversible potential. Allison et al. (1972) attributed the behavior to the decomposition of cupric xanthate. 

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