Reduced standard-state chemical potential temperature

The thermodynamic quantity 0y is a reduced standard-state chemical potential difference and is a function only of T, P, and the choice of standard state. The principal temperature dependence of the liquidus and solidus surfaces is contained in 0 j. The term is the ratio of the deviation from ideal-solution behavior in the liquid phase to that in the solid phase. This term is consistent with the notion that only the difference between the values of the Gibbs energy for the solid and liquid phases determines which equilibrium phases are present. Expressions for the limits of the quaternary phase diagram are easily obtained (e.g., for a ternary AJB C system, y = 1 and xD = 0 for a pseudobinary section, y = 1, xD = 0, and xc = 1/2 and for a binary AC system, x = y = xAC = 1 and xB = xD = 0). 

With the standard state for each component chosen as the pure component in the phase of interest and at the temperature of interest, Chang et al. (4-) have discussed three thermodynamic sequences for the calculation of the reduced standard state chemical potentials. The pathways for each sequence are shown in Figure 2. 

Four different methods were presented to determine the reduced standard state chemical potential change and applied to the Ga-Sb system. It is common practice to use Equation 7 and a solution model representing the stoichiometric liquid activities to determine 0. The solution model parameters are then estimated from a fit of the binary phase diagram. It has been shown that this procedure can lead to large errors in the value of 0. The use of Equation 9, however, gave the correct temperature dependence of 0 and the inclusion of activity measurements in the data base replicated the recommended values of 0Tp. 

We now have the foundation for applying thermodynamics to chemical processes. We have defined the potential that moves mass in a chemical process and have developed the criteria for spontaneity and for equilibrium in terms of this chemical potential. We have defined fugacity and activity in terms of the chemical potential and have derived the equations for determining the effect of pressure and temperature on the fugacity and activity. Finally, we have introduced the concept of a standard state, have described the usual choices of standard states for pure substances (solids, liquids, or gases) and for components in solution, and have seen how these choices of standard states reduce the activity to pressure in gaseous systems in the limits of low pressure, to concentration (mole fraction or molality) in solutions in the limit of low concentration of solute, and to a value near unity for pure solids or pure liquids at pressures near ambient. 

Equation 7.15 implies that, for an electrochemical reaction involving a redox reaction, there exists an electrode potential that is related to the chemical potentials of the reactants and the reaction products and is calculated by this equation. This electrochemical potential is called the redox potential . This potential is positive for an oxidation reaction, where a constituent involved will gain in valency, while it is negative for a reduction reaction, where the valency is reduced for the constituent. In the standard thermodynamic state (i.e., for an ideal condition where each of the species is 1 mol at standard temperature and pressure), the standard redox potential is... 

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