Chemical Thermodynamics of Mixed Phases
Phase, components, solution and mixtures, molar fraction, partial molar properties, mean properties, number of independent components. Gibbs-Duhem relation. Chemical potential of a component: entropy of mixing ideal gases, μi = μiχo + RT ln (fχ χ) for various composition measures χ, corresponding standard potentials μiχo. Microscpic interpretation of μi, ideal mixtures, nonideality. Phase equilibria: concept of degree of freedom, phase diagrams. Between phases of a pure compound Clausius-Clapeyron P(T). For mixed phases Gibb´s phase rule. Solvent equilibria: reduction of vapour pressure, increase of boiling point, osmotic pressure. Solution equilibria: solubility of a gas (Henry´s law), of a solid. General mixed-phase equilibria: distribution of a miscible compound (Nernst´s law), solubility diagrams, vapour pressure and boiling point diagrams. Chemical equilibria: stochiometry coefficients νi, reaction number ζ (dni = νidζ), reaction properties ΔrY = ∂y/∂ζ. Reaction affinity A = – ΔrG = – Σ νi μi . Homogeneous reactions: equilibrium constants Kp(T), Kx(T,P), Kc(T), their temperature (vant´t Hoff) and pressure (Planck, van Laar) dependence. Calculations of chemical equilibria: Standard heat ΔrHo and entropy ΔrSo of reaction, of formation, of combustion.
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