By N. D. Chatterjee
Thermodynamic remedy of mineral equilibria, an issue imperative to mineralogical thermodynamics, could be traced again to the tum of the century, while J. H. Van't Hoff and his affiliates pioneered in utilizing thermodynamics to the mineral assemblages saw within the Stassfurt salt deposit. even if different popular researchers joined forces to enhance the topic - H. E. Boeke even attempted to popularize it via giving an outline of the early advancements in his "Grundlagen der physikalisch-chemischen Petrographie", Berlin, 1915 - it remained, ordinarily, an esoteric topic for almost all of the modern geological neighborhood. noticeable that manner, mineralogical thermodynamics got here of age over the past 4 many years, and advanced very speedily right into a mainstream self-discipline of geochemistry. It has contributed significantly to our figuring out of the section equilibria of mineral structures, and has helped placed mineralogy and petrology on a company quantitative foundation. within the wake of those advancements, educational curricula now require the scholars of geology to take a path in simple thermodynamics, often provided via the departments of chemistry. construction on that beginning, a supplementary path is usually provided to familiarize the scholars with varied mineralogical functions of thermo dynamics. This e-book attracts from the author's event in giving this kind of direction, and has been adapted to cater to those that have had a prior publicity to the fundamental ideas of chemical thermodynamics.
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Additional info for Applied Mineralogical Thermodynamics: Selected Topics
6 Excess Molar Properties of Mixing An excess molar property of mixing is the difference between the actual property and that of the ideal solution. Alternatively, it may be defined as Y m - yidm. 71a) Y denoting any molar property of a real solution. Thus, yexm is a measure of the deviation of a real solution from its hypothetical ideal behavior. Applying this general relation to Gibbs energy, Gex + X2gex m = G - Gid = G m - Gid m = (l-X2)gexl ~ ~2 = RT[(1-X2)lnYl + X2lnY2]. 7 delineates, in a general manner, the composition dependence of G m and Gidm (above) and Gexm (below) for a solution at constant T and P.
Note that WG,i equals RTlnyt Note that the component at infinite dilution appears first in succession. 86) Because of its popularity in mineralogy, we shall mostly use the Margules equation in Chapters 8 and 9. It is emphasized though that the Gexill of a solution may be alternatively expressed in terms of the Margules or RedlichKister equation, since the former is a special case of the latter. 89) RTlnY2 = [WG,21 + 2(WG,12 - W G,21)X2](l-X2)2. 8 (bottom) shows the composition dependence of the RTlnYi terms for the same solution represented in the upper part of that diagram.
3 A schematic plot of the functional dependence between flj and InXj at constant T and P (adapted from Froese 1981). The heavy curve depicts the behavior of a nonideal solution. + RTlnaj(R). 66a) Solving for aj(H), ai(H) = ai(R) . 66) As emphasized earlier, in the subsequent chapters, we shall extensively use the Raoultian activity. The corresponding aj-Xj and 'Yj-Xj relations are delineated in Fig. 4. As Xj~l and 'Yj~l, so does aj. There is usually a short range of Xj in which 'Yj=l (cf. Fig. 3), and therefore, aj = Xj; this is the range of validity of Raoult's law.
Applied Mineralogical Thermodynamics: Selected Topics by N. D. Chatterjee