The critical point of mixtures requires a more intricate set of conditions to hold than those at a pure-fluid critical point. In contrast to the pure-fluid case, in which the critical point occurs at a unique point, mixtures have additional thermodynamic degrees of freedom. They, therefore, possess a critical line which defines a locus of critical points for the mixture. At each point along this locus, the mixture exhibits a critical point with its own composition, temperature, and pressure. In this chapter we investigate the critical behavior of binary mixtures, since higher-order systems do not bring significant new considerations beyond those found in binaries. We deal first with mixtures at finite compositions along the critical locus, followed by consideration of the technologically important case involving dilute mixtures near the solvent’s critical point. Before taking up this discussion, however, we briefly describe some of the main topographic features of the critical line of systems of significant interest: those for which nonvolatile solutes are dissolved in a solvent near its critical point. The critical line divides the P–T plane into two distinctive regions. The area above the line is a one-phase region, while below this line, phase transitions can occur. For example, a mixture of overall composition xc will have a loop associated with it, like the one shown in figure 4.1, which just touches the critical line of the mixture at a unique point. The leg of the curve to the “left” of the critical point is referred to as the bubble line; while that to the right is termed the dew line. Phase equilibrium occurs between two phases at the point where the bubble line at one composition intersects the dew line; this requires two loops to be drawn of the sort shown in figure 4.1. A question naturally arises as to whether or not all binary systems exhibit continuous critical lines like that shown. In particular we are interested in the situation involving a nonvolatile solute dissolved in a supercritical fluid of high volatility.
Derivation of the Critical Point Scaling Hypothesis Using Thermodynamics Only
