STABILITY AND FLUCTUATIONS BASED ON ENTROPY PRODUCTION

The random motion of molecules causes all thermodynamic quantities such as temperature, concentration and partial molar volume to fluctuate. In addition, due to its interaction with the exterior, the state of a system is subject to constant perturbations. The state of equilibrium must remain stable in the face of all fluctuations and perturbations. In this chapter we shall develop a theory of stability for isolated systems in which the total energy U, volume V and mole numbers Nk are constant. The stability of the equilibrium state leads us to conclude that certain physical quantities, such as heat capacities, have a definite sign. This will be an introduction to the theory of stability as was developed by Gibbs. Chapter 13 contains some elementary applications of this stability theory. In Chapter 14, we shall present a more general theory of stability and fluctuations based on the entropy production associated with a fluctuation. The more general theory is applicable to a wide range of systems, including nonequilibrium systems. 

---