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

Thermodynamics of Pure Compounds

Thermodynamics of Pure Compounds

State, state functions and variables, partial derivatives as typical for measurement. Types of systems, examples. Internal energy and processes (1st 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 cp and cv; typical cp(T) of some compounds. Ideal gas, its equation of state, cv 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 (2nd law): from (differential) heat to differential entropy via integrating factor T, determination of s by integration of cp(T)/T. 2nd Law: properties of s(u) for a single system, maximisation of s=s1+s2 when systems are combined. Irreversibility. Entropy of melting, vaporisation. 3rd 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 cP as second derivatives. Maxwell-Relations. Description of experiments generally by some (∂z/∂x)y., its systematic reduction to α, κ, Cp. Examples: internal pressure (∂U/∂V)S, (∂H/∂P)T, Joule-Thompson coefficient, (∂S/∂T)P = Cp/T, Cp-Cv.

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.