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Thermodynamic oxygen transfer

FIGURE 3.1 Thermodynamic oxygen transfer potentials. DMDO, dimethyldioxirane Ac, CH3C(0) DMSO, dimethyl sulfoxide DMS, dimethyl sulfide. [Pg.76]

TOP Thermodynamic oxygen transfer potential, according to J Am Chem Soc 2004 126 996 TS Transition state... [Pg.110]

Figure 25.10 Selective oxygen transfer through thermodynamic control. Figure 25.10 Selective oxygen transfer through thermodynamic control.
With increasing thickness x of the oxide layer, the difference (Cy — Cy) increases, that is, the driving force in the process is needed for the difiusion in the oxide. On the other hand, the oxygen activity on the wustite surface approaches equilibrium with the atmosphere ao KiipCOz pCO), that is, the oxygen transfer needs only a lessening part of the thermodynamic driving force (Fig. 8). [Pg.642]

Table 4-1 lists some rate constants for acid-base reactions. A very simple yet powerful generalization can be made For normal acids, proton transfer in the thermodynamically favored direction is diffusion controlled. Normal acids are predominantly oxygen and nitrogen acids carbon acids do not fit this pattern. The thermodynamicEilly favored direction is that in which the conventionally written equilibrium constant is greater than unity this is readily established from the pK of the conjugate acid. Approximate values of rate constants in both directions can thus be estimated by assuming a typical diffusion-limited value in the favored direction (most reasonably by inspection of experimental results for closely related... [Pg.149]

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. [Pg.429]

In summary for non-metal transfer situations chemical thermodynamics is a useful guide to probable behaviour. The transfer of a non-metal, X, dissolved in a molten metal, M to another metal M", will depend on the relative free energies of formation of M X and M X (see Section 7.6). Thus sodium will give up oxygen to Zr, Nb, Ti and U, as the free energy of oxide formation of these metals is greater than that for sodium on the other hand, sodium will remove oxygen from oxides of Fe, Mo and Cu unless double oxides are formed. [Pg.432]


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