The critical state and its thermodynamic stability

Abstract

The Gibbs approach to study of the critical state is expanded. It is noted that the well known critical state condition D=0 was obtained by Gibbs as a necessary condition for a non-zero solution of a system of homogeneous linear equations and defines a line of spinoidal solutions. To determine the critical point on this line the explicit form of solutions of a system of homogeneous equations is considered and their relationship to the slope of the phase equilibrium line is established. For the condition D=0 four possible cases of critical system thermodynamic behavior are considered. The relationship between each of these cases and the slope of the phase equilibrium line at the critical point is established. General thermodynamic stability conditions for the critical point are considered as a function of the type of critical behavior at the point. It is shown that one of the consequences of critical point stability is a merger of the binodal line with the spinodal at the critical point.