Lecture 16 Phase Transformations in Binary Mixtures 讲座1相转换的二进制的混合物.pptVIP

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Lecture 16 Phase Transformations in Binary Mixtures 讲座1相转换的二进制的混合物.ppt

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Lecture 16 Phase Transformations in Binary Mixtures 讲座1相转换的二进制的混合物

Lecture 17. Phase Transformations (Phase Separation) in Binary Mixtures (Ch. 5) A mixture is homogeneous when its constituents are intermixed on the atomic scale (it is also called solution). A mixture is heterogeneous when its contains two or more distinct phases, such as oil and water that do not mix at normal T, each phase has different concentrations of intermixed atoms/molecules (phase separation). Our goal is to find out how the free energy minimum principle governs the behavior of mixtures. (b) mixing occurs at fixed T,P within a fixed volume V. In this case, it does not matter which free energy we minimize - both F and G work equally well. T x P P = const planes Phase diagram of a binary mixture Boundary between different phases A simplified picture: Binary Mixtures (a) binary mixtures. The phase diagram for such a system has an extra dimension – x. - a mixture will seek the state of equilibrium by minimizing this combination of its internal energy and entropy. We need to analyze both terms. Interaction Energy in Binary Mixtures Each atom has p nearest neighbors. Let uAA, uAB, uBB represent the bond energy between A-A, A-B, and B-B pairs, respectively. On the average, an A atom is involved in p(1-x) interactions of A-A type and px interactions of A-B type. The average interaction energy per A atom: The average interaction energy per B atom: The total interaction energy: Let’s assume that the mixture is in a solid state, both species share the same lattice structure. Consider NA atoms of species A and NB =N - NA atoms of species B (x = NB/N). U x 1 0 The overall shape of U(x) depends on the interactions between different species: (the factor ? corrects the fact that each bond has to be counted just once) Ideal and Non-Ideal Mixtures U x 1 0 As we’ll see, the fact that U has an upward bulge will have important consequences for phase separation in this mixture. Ideal mixtures – the molecules A and B are of the same size and interactions A-A, A-B, an