Solvent selection is an important factor in chemical process efficiency, profitability, and environmental impact. Prediction of solvent phase behavior will allow for the identification of novel solvent systems that could offer some economic or environmental advantage. A modified cohesive energy density model is used to predict the solid-liquid-equilibria for multifunctional solids in pure and mixed solvents for rapid identification of process solvents for design of crystallization processes. Some solubility data at several temperatures are also measured to further test the general applicability of the model. Gas-expanded liquids have potential environmentally advantageous applications as pressure tunable solvents for homogeneous and heterogeneous catalytic reactions and as novel solvent media for anti-solvent crystallizations. The phase behavior of some carbon dioxide/organic binary systems is measured to provide basic process design information. Solvent selection is also an important factor in the anti-solvent precipitation of solid compounds. The influence of organic solvent on the solid-liquid equilibria for two solid pharmaceutical compounds in several carbon dioxide expanded solvents is explored. A novel solvent system is also developed that allows for homogeneous catalytic reaction and subsequent catalyst sequestration by using carbon dioxide as a miscibility switch. The fundamental biphasic solution behavior of some polar organics with water and carbon dioxide are investigated.