Introduction to Chemical Thermodynamics

10 Lectures. First Year. Michaelmas Term.

Lecture Synopsis

  1. Introduction and Background. Le Chatelier's Principle. Equations of state. Systems and their surroundings. Work and heat as currencies of energy.
  2. The First Law.The conservation of energy: Internal energy. State functions and exact differentials. Expansion work. Reversible and irreversible changes. Heat capacity. Enthalpy.
  3. Thermochemistry. The standard state. Standard enthalpy of a phase transition. Standard reaction enthalpy. Standard enthalpy of formation. Temperature dependence of reaction enthalpy.
  4. The Second Law. The direction of spontaneous change: Entropy. The condition for equilibrium. Entropy of a phase transition. Variation of entropy with temperature and pressure. The third law. Statistical interpretation of entropy.
  5. Free Energy. The direction of spontaneous change: Helmholtz and Gibbs free energies. Available work. Fundamental equations and Maxwell relations. Variation of Gibbs free energy with temperature and pressure.
  6. Phase Equilibria. The condition for phase equilibrium. Clapeyron and Claussius-Clapeyron equations. One-component phase diagrams.
  7. Chemical Equilibria. Variation of Gibbs free energy with composition: The chemical potential of a component in a mixture. The extent of reaction. The condition for chemical equilibrium. Gibbs free energy of formation. Gibbs free energy of reaction. The reaction quotient. The equilibrium constant and its temperature dependence.

Lecture Handouts

  1. Lecture synopsis and problem set (PDF).
  2. Lecture handout (PDF).

Bibliography

For a quick summary of the working equations of thermodynamics, and how they are derived, see the lecture handout. For a discussion of the concepts, see:

  1. P. W. Atkins and J. de Paula, Atkins' Physical Chemistry (7th edition, OUP, 2001); Chapters 1 to 9.
  2. E. B. Smith, Basic Chemical Thermodynamics (4th edition, OUP, 1990); Chapters 1 to 8.