Partial pressure phase diagrams, construction

For any particular system, a graph can be constructed using the concentration of the solute in the liquid phase (Ca) and the concentration or partial pressure of the solute in the gas phase (Pa) as the abscissa and ordinate, respectively. A line indicating the equilibrium concentrations of the solute in the gas and solvent drawn on this graph, results in an equilibrium diagram. 

Partial pressure as a variable. As mentioned in 2.1, many types of thermodynamic variables may be used in the construction of phase diagrams. The various rules of construction, based on the laws of chemical thermodynamics, which apply to the different types of phase diagrams have been discussed in several books and papers (for instance, Pelton and Schmalzried 1973, Okamoto 1991, Pelton 1991). Following a classification proposed by Pelton, the various, bidimensional, phase diagrams may be subdivided into three types as follows ... 

Based on the standard Gibbs free energy of the various oxides, three triple points can be calculated WO2.72. WO2.9, WO2 at about 600°C, W02,9, WO3, WO2 at about 270°C, and WO2, WO2.72, W at 1480°C. Using this data, a phase diagram can be constructed. The stability of the various oxides is shown in Fig. 8.2 with respect to the partial pressures of H2O and H2, and temperature. Because aU of these compositions are equilibrium compositions, any of them can be produced simply by annealing W or WO3 at the given partial pressure ratio and temperature. 

The ranges of Eh and pH over which a particular chemical species is thermodynamically expected to be dominant in a given aqueous system can be displayed graphically as stability fields in a Pourbaix diagram,10-14 These are constructed with the aid of the Nernst equation, together with the solubility products of any solid phases involved, for certain specified activities of the reactants. For example, the stability field of liquid water under standard conditions (partial pressures of H2 and 02 of 1 bar, at 25 °C) is delineated in Fig. 15.2 by... 

So far we have discussed the basic concept of non-stoichiometry without showing real examples. Here we shall consider case studies in order to understand the non-stoichiometry appearing in various kinds of substances. To construct phase diagrams which contain non-stoichiometric compounds, it is indispensable to know the relationship between the deviation from stoichiometry <5, the partial pressure of coexisted gas, (for diatomic gases),... 

When a metal reacts with a gas containing more than one oxidant, a number of different phases may form depending on both thermodynamic and kinetic considerations. Isothermal stability diagrams, usually constructed with the logarithmic values of the activities or partial pressures of the two non-metallic components as... 

In Fig. 4-9 a constant-temperature diagram for this system has been constructed in which the ordinate is the partial pressure of the components, and the abcissa is the mol fraction of ether in the mixture. This mol fraction is the mols of the ether in the combined liquid phases divided by the total mols of ether and water in all of the liquid present. 

Take, for example, the plot of G versus temperature for elemental sulfur, represented by the bottom diagram in Figure 2.1. We know from experiments and observation that there are four phases we have to consider for sulfur two solid forms (a low-temperature orthorhombic form, R, and high-temperature monoclinic form, M), liquid (L), and vapor (or gas, V). The lines of G versus T for each phase, which are partially solid and continue on as dashed lines, are constructed at constant pressure using Eq. (2.10),... 

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