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

State, state functions and variables, partial derivatives as typical for measurement. Types of systems, examples. Internal energy and processes (1^st Law): heat, (volume-)work, chemical work across appropriate walls change internal energy. Work on ideal gas under isothermal or adiabatic conditions. Internal energy of a pure compound: microscopic interpretation. Free energy. Enthalpy, its utility for processes at constant pressure. Heat capacities c_p and c_v; typical c_p(T) of some compounds. Ideal gas, its equation of state, c_v depending on microscopic degrees of freedom. Van-der-Waals gas. Heat of melting, vaporisation. Thermochemistry: Hess' law, heat of formation, reaction enthalpy. Standards, transfer terms from standard to actual state. Entropy and equilibrium (2^nd law): from (differential) heat to differential entropy via integrating factor T, determination of s by integration of c_p(T)/T. 2^nd Law: properties of s(u) for a single system, maximisation of s=s₁+s₂ when systems are combined. Irreversibility. Entropy of melting, vaporisation. 3^rd Law. — Mathematical intermezzo: f(x,y), partial derivatives, total differential df, Schwartz´ theorem, reconstruction of (relative) f by integrating partial derivatives. Slope of f along paths [for example f(x,y) =const giving (∂x/∂y)_f, or path g(x,y)=const giving (∂f/∂x)_g ]. Legendre-transformation of f(x,y), back transformation; examples. Thermodynamic relationships: thermodynamic potentials or Gibbs functions U, F, H, G as Legendre transforms when presented in terms of natural variables, state functions such as T(s,v,n) as first derivatives, material properties such as c_P as second derivatives. Maxwell-Relations. Description of experiments generally by some (∂z/∂x)_y., its systematic reduction to α, κ, C_p. Examples: internal pressure (∂U/∂V)_S, (∂H/∂P)_T, Joule-Thompson coefficient, (∂S/∂T)_P = C_p/T, C_p-C_v.

General textbooks of Physical Chemistry:

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

Monographies on chemical thermodynamics

"Chemische Thermodynamik", Bd. 4 des Lehrwerks Chemie (Lehrbuch 4 und Arbeitsbuch 4), VEB Deutscher Verlag für Grundstoffindustrie, 1985.
U. Nickel, "Lehrbuch der Thermodynamik" (Neuerscheinung), 2. Aufl., PhysChem Verlag 2011,
           ISBN 978-3-937744-06-3
H. + J. Rau, "Chemische Gleichgewichts-Thermodynamik", Springer Verlag, Heidelberg,
           ISBN: 3 540 67065 3
Herbert B. Callen, Thermodynamics and an Introduction to Thermostatistics, Wiley 1985 ff.,
           ISBN: 0 471 86256 8.
Arnold Sommerfeld, "Thermodynamik und Statistik", Harry Deutsch Verlag, Bd. 5, Vorlesungen über Theoretische Physik 1988,
           ISBN: 3 87144-378.