A Chemical Test of Critical Point Isomorphism: Reactive Dissolution of Ionic Solids in Isobutyric Acid + Water near the Consolute Point

Binary liquid mixtures having a consolute point can be used as solvents for chemical reactions. When excess cerium(IV) oxide is brought into equilibrium with a mixture of isobutyric acid + water, and the concentration of cerium in the liquid phase is plotted in van’t Hoff form, a straight line results for temperatures sufficiently in excess of the critical solution temperature. Within 1 K of the critical temperature, however, the concentration becomes substantially suppressed, and the van’t Hoff slope diverges toward negative infinity. According to the phase rule, one mole fraction can be fixed. Given this restriction, the temperature behavior of the data is in exact agreement with the predictions of both the principle of critical point isomorphism and the Gibbs–Helmholtz equation. In addition, we have determined the concentration of lead in the liquid phase when crystalline lead(II) sulfate reacts with potassium iodide in isobutyric acid + water. When plotted in van’t Hoff form, the data lie on a straight line for all temperatures including the critical region. The phase rule indicates that two mole fractions can be fixed. With this restriction, the data are in exact agreement with the principle of critical point isomorphism.