A chemical test of the principle of critical point universality: The solubility of nickel (II) oxide in isobutyric acid + water near the consolute point

Abstract

A mixture of isobutyric acid + water has an upper consolute point at 38.8 mass % isobutyric acid and temperature near 26 °C. Nickel (II) oxide dissolves in this mixture by reacting with the acid to produce water and nickel isobutyrate. The solubility of nickel (II) oxide in isobutyric acid + water has been measured as a function of temperature at compositions, 25, 38.8, and 60 mass % isobutyric acid. For values of the temperature, T, which were at least 2 K in excess of the liquid-liquid phase transition temperature, the measured values of the solubility, s, lie on a straight line when plotted in van't Hoff form with ln s versus 1∕T. The slope, (∂ln s∕∂(1∕T)), of the line is negative indicating that the dissolution reaction is endothermic. When the temperature was within 2 K of the phase transition temperature, however, (∂ln s∕∂(1∕T)) diverged toward negative infinity. The principle of critical point universality predicts that when excess solid nickel (II) oxide is in dissolution equilibrium with liquid isobutyric acid + water, (∂ln s∕∂(1∕T)) should diverge upon approaching the consolute point along the critical isopleth at 38.8 mass % isobutyric acid. As determined by the sign of the enthalpy of solution, the sign of this divergence is expected to be negative. Not only do our experiments confirm these predictions, but they also show that identical behavior can be observed at both 25 and 60 mass % isobustyric acid, compositions which lie substantially to either side of the critical composition.