Gibbs energy, phase stability

TABLE 2.1 Stability of the QM-Cytosine Conjugates Relatively to Free Reactants in the Gas Phase (AGgas) and in Aqueous Solution (AGaq). Activation Gibbs Energy for Their Decomposition into QM and Cytosine (AGjjev aq)... 

The effect of the aqueous medium on the reactivity and on the stability of the resulting adducts has been investigated to assess which adduct arises from the kinetically favorable path or from an equilibrating process. The calculations indicate that the most nucleophilic site of the methyl-substituted nucleobases in the gas phase is the guanine oxygen atom, followed by the adenine N1, while other centers exhibit a substantially lower nucleophilicity (see activation Gibbs energies in Table 2.2). 

ArV is not necessarily positive, and to compare the relative stability of the different modifications of a ternary compound like AGSiOs the volume of formation of the ternary oxide from the binary constituent oxides is considered for convenience. The pressure dependence of the Gibbs energies of formation from the binary constituent oxides of kyanite, sillimanite and andalusite polymorphs of A SiOs are shown in Figure 1.10. Whereas sillimanite and andalusite have positive volumes of formation and are destabilized by pressure relative to the binary oxides, kyanite has a negative volume of formation and becomes the stable high-pressure phase. The thermodynamic data used in the calculations are given in Table 1.7 [3].1... 

It should be remembered that the CALPHAD approach is based on the hypothesis that, for all the phases and structures existing across the complete alloy system, entire Gibbs energy vs. composition curves may be constructed even by extrapolation into regions where they are unstable or metastable. A particular case concerns the pure component elements for which the relative Gibbs energy for the different crystal structures (the so-called lattice stabilities) must also be established and defined as a function of temperature (and pressure). 

Figure 7.4 Gibbs free energy curves and phase stability relations for two binary mixtures with complete miscibility of components (types I, II, and III of Roozeboom, 1899).

Figure 7J Gibbs free energy curves and T-X phase stability relations between a phase with complete miscibility of components (silicate melt L) and a binary solid mixture with partial miscibility of components (crystals ]8). 

Figure 7,8 Gibbs free energy curves and T-X phase relations for an intermediate compound (C), totally immiscible with pure components. Column 1 Gibbs free energy relations leading to formation of two eutectic minima separated by a thermal barrier. Column 2 energy relations of a peritectic reaction (incongruent melting). To facilitate interpretation of phase stability fields, pure crystals of components 1 and 2 coexisting with crystals C are labeled y and y", respectively, in T-X diagrams same notation identifies mechanical mixtures 2-C and C-1 in G-X plots.

Here the first term represents the lattice stability components of the phase , the second term the Gibbs energy contribution arising from cluster calculations and the third term is the excess Gibbs energy expressed in the form of a standard Redlich-Kister polynomial (see Chapter 5). 

---