Steve Patitsas (U)
A nonequilibrium thermodynamic theory demonstrating an induction effect of a statistical nature will be presented. We have shown that this thermodynamic induction can arise in a class of systems that have variable kinetic coefficients (VKC). In particular if a kinetic coefficient associated with a given thermodynamic variable depends on another, faster, thermodynamic variable then we have derived an expression that can predict the extent of the induction. The amount of induction is shown to be proportional to the square of the generalized driving force. This result constitutes an extension of the Onsager symmetry relations to the nonlinear realm. We note an important sign difference. While the entire system approaches thermodynamic equilibrium, some variables may be induced to leave thermodynamic equilibrium. Some subsystems may move to lower entropy configurations, for sustained periods of time, without violating the second law of thermodynamics. Also, induction allows the entire system to approach equilibrium faster than expected. Thus we present a nonequilibrium version of Le Chatelier's principle. We have also developed a variational approach, based on optimizing entropy production, in a certain sense. On the question of resolving whether entropy production is minimized or maximized, we conclude neither, but we produce a function that is maximized. The maximization occurs while the fast variables are quasistationary. Thus, the stationary states of Prigogine, introduced in the context of the minimum entropy production principle, are still very useful. Finally, we will discuss possible schemes directed towards discovering experimental evidence for thermodynamic induction, including manipulation of individual atoms using a scanning tunnelling microscope.
Steve Patitsas (U)