Internal Variable Theory Formulated by One Extended Potential Function

Abstract

AbstractIn the kinetic rate laws of internal variables, it is usually assumed that the rates of internal variables depend on the conjugate forces of the internal variables and the state variables. The dependence on the conjugate force has been fully addressed around flow potential functions. The kinetic rate laws can be formulated with two potential functions, the free energy function and the flow potential function. The dependence on the state variables has not been well addressed. Motivated by the previous study on the asymptotic stability of the internal variable theory by J. R. Rice, the thermodynamic significance of the dependence on the state variables is addressed in this paper. It is shown in this paper that the kinetic rate laws can be formulated by one extended potential function defined in an extended state space if the rates of internal variables do not depend explicitly on the internal variables. The extended state space is spanned by the state variables and the rate of internal variables. Furthermore, if the rates of internal variables do not depend explicitly on state variables, an extended Gibbs equation can be established based on the extended potential function, from which all constitutive equations can be recovered. This work may be considered as a certain Lagrangian formulation of the internal variable theory.