Near-infrared spectroscopic measurements of volume expansion and composition of CO2-expanded ethyl acetate, acetone, tetrahydrofuran, acetonitrile, methanol-OD, and dimethyl sulfoxide

Abstract

CO2-expanded liquid (CXL) is a mixture of organic solvent with high-pressure CO2 whose volume is increased by CO2 dissolved in it. CXLs have attracted attention as tunable solvents, because the solvent properties can be widely controlled by the pressure. The volume expansion and the solubility of CO2 were measured by near-infrared spectroscopy for 6 CXLs at various pressures up to 55bar and 40°C. The molarity of organic solvent was determined from the absorbance of the 3ν and 2ν+δ bands, and that of CO2 was obtained from the area of the 3ν3 band, whose peak shifted to higher frequency with increasing pressure due to a decrease in the molecular interaction around CO2. The expansion coefficient was shown to be an increasing function of the pressure with larger slope at higher pressure, and the mole fraction of CO2 in the liquid phase was an almost linearly increasing function of the pressure. The results were in quantitative agreement with the literature data measured by conventional sampling method, indicating the validity of the spectroscopic method.