Münster Arnold. Classical Thermodynamics

The Laws of thermodynamics
Definitions.
Classical formulation of the Laws.
The First Law. Internal energy.
The Second Law. Entropy and absolute temperature.
Refrigerators and heat pumps.
Carathéodory’s axioms.
Definitions.
Empirical temperature.
The First Law.
Interlude: Pfaff differentials.
The Second Law applied to quasi-static processes.
Empirical definition of U, S, and T.
Measurement of very low temperatures.
The Second Law applied to non-static processes.
Generalization of the Second Law for open systems and chemical reactions.
The problem.
General formulation of the Second Law.
General conditions for equilibrium and stability
Discussion of the equilibrium concept. Internal parameters.
Gibbs’ equilibrium conditions.
The stability conditions.
Thermodynamic potentials and Massieu—Planck functions
Interlude: Legendre transformations. Homogeneous functions and Euler’s theorem.
The fundamental equation. Extensive and intensive parameters. Equations of state. The Gibbs—Duhem equation.
Thermodynamic potentials.
Massieu—Planck functions.
Transformation of the equilibrium and stability conditions.
Gibbs—Helmholtz equations and Maxwell’s relations.
Conversion of partial derivatives. Method of Jacobi determinants. The Joule—Thomson effect.
Mean molar and partial molar quantities.
Heterogeneous equilibria without chemical reactions
General equilibrium conditions for heterogeneous systems.
Membrane equilibria. Osmotic pressure.
The phase rule.
Phase reactions.
Invariant and univariant equilibria.
Bivariant and multivariant equilibria.
Chemical equilibria
General equilibrium conditions.
Homogeneous reactions. The law of mass action.
Heterogeneous reactions.
The progress variable. Affinity.
The thermodynamic calculation of chemical reactions.
Nemst’s heat theorem. The unattainability of the absolute zero. Zero point entropies.
Stability conditions
Statement of the problem. Gibbs’ criterion.
The stability conditions in the energy representation.
Transformation of the stability conditions.
Stability conditions for heterogeneous systems.
The Le Châtelier—Braun principle.
The stability of chemical equilibria.
Critical phases. Transitions of higher order
Definition and properties of critical phases.
Gibbs’ equations for critical phases.
Transformation of the equations for critical phases. Further properties of critical phases.
Transitions of higher order. The Ehrenfest equations.
Tisza’s theory. I: The general basis.
Tisza’s theory. II: Formulation of the stability conditions.
Tisza’s theory. III: Critical points and higher-order transitions.
Solids
The strain tensor.
The stress tensor.
The fundamental equation and thermal equations of state.
Thermodynamic potentials and Maxwell’s relations.
Symmetry properties of solids.
Systems in an electric field
Electrostatic work.
The fundamental equation for a dielectric in an electric field.
Thermodynamic potentials.
Electrostriction.
The electrocaloric effect.
Piezoelectricity.
Ferroelectricity.
Systems in a magnetic field
Magnetostatic work.
The fundamental equation for a system in a magnetic field. Thermodynamic potentials.
The magnetocaloric effect.
Superconduction.
Electrochemical systems
Definition and general properties of electrochemical systems.
General conditions for electrochemical equilibrium.
Solutions of strong electrolytes.
Membrane equilibria of electrolyte solutions.
Galvanic cells.
Gravitational field. Centrifugal field. The determination of molecular weights
Systems in a gravitational field.
Systems in a centrifugal field.
The determination of molecular weights.
Problems
Hints for solving the problems
Solutions to the problems