Abstract
Thermodynamic properties associated with the interaction of TiCl4 with supercritical CO2 have been determined using flow calorimetry. Incorporation of an ultrasonic densitometer in the calorimeter system increases the usefulness of the procedure. Titanium tetrachloride was shown to be highly soluble in supercritical CO2 near the CO2 critical point. Titanium tetrachloride exhibited excess enthalpy of mixing and vapor-liquid equilibrium behavior similar to those of organic hydrocarbons in supercritical CO2. Solubility of TiCl4 in supercritical CO2 appeared unusual in view of the low solubility commonly observed for ionic metal salts in supercritical fluids. The solubility of TiCl4 is ascribed to the coincidence of valence charge and coordination number of the titanium. This equality of valence and coordination allows TiCl4 to exist as discrete molecules. Solution densities measured in the calorimetric apparatus varied nonlinearly with solution composition.
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