Humboldt-Universität zu Berlin - Faculty of Mathematics and Natural Sciences - Department of Chemistry

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.


G. Wedler, "Lehrbuch der Physikalischen Chemie", Wiley-VCH, 1997.
P. W. Atkins, "Physikalische Chemie", Wiley-VCH, 2002, "Physical Chemistry", Oxford University Press, 2000.
H. Kuhn und H.D. Försterling, "Principles of Physical Chemistry", Wiley 1999.


Monographies on chemical thermodynamics

IUPAC: "Größen, Einheiten und Symbole in der Physikalischen Chemie", VCH 1995.
"Chemische Thermodynamik", Bd. 4 des Lehrwerks Chemie (Lehrbuch 4 und Arbeitsbuch 4), VEB Deutscher Verlag für Grundstoffindustrie, 1985.
U. Nickel: "Lehrbuch der Thermodynamik", Carl Hanser Verlag 1995.
H. + J. Rau:, "Chemische Gleichgewichts-Thermodynamik", Springer Verlag, Heidelberg,
Herbert B. Callen: Thermodynamics and an Introduction to Thermostatistics, Wiley 1985.
Arnold Sommerfeld, "Thermodynamik und Statistik", Harry Deutsch Verlag, Bd. 5, Vorlesungen über Theoretische Physik 1988.