The gas–liquid phase-transition singularities in the framework of the liquid-state integral equation formalism

Abstract

The singularities of various liquid-state integral equations derived from the Ornstein-Zernike relation and its temperature derivatives, have been investigated in the liquid-vapor transition region. As a general feature, it has been found that the existence of a nonsolution curve on the vapor side of the phase diagram, on which both the direct and the total correlation functions become complex-with a finite isothermal compressibility-also corresponds to the locus of points where the constant-volume heat capacity diverges, in consonance with a divergence of the temperature derivative of the correlation functions. In contrast, on the liquid side of the phase diagram one finds that a true spinodal (a curve of diverging isothermal compressibilities) is reproduced by the Percus-Yevick and Martynov-Sarkisov integral equations, but now this curve corresponds to states with finite heat capacity. On the other hand, the hypernetted chain approximation exhibits a nonsolution curve with finite compressibilities and heat capacities in which, as temperature is lowered, the former tends to diverge.