33. In situ measurement of liquid-liquid equilibria by medium field nuclear magnetic resonance

Anne Friebel, Agnes Fröscher, Kerstin Münnemann, Erik von Harbou, Hans Hasse, Fluid Phase Equilibria, (2017), 438, 44–52, DOI: 10.1016/j.fluid.2017.01.027

A new method for non-invasive measurement of liquid-liquid equilibria (LLE) using a compact medium field nuclear magnetic resonance (NMR) spectrometer is presented. Mixing of all components, phase separation, and analysis of the composition of the coexisting phases is performed in situ in an NMR glass tube. Thus, the experimental effort is reduced and errors caused by sampling are eliminated. Furthermore, calibration of the analysis method is not necessary as quantitative information is obtained directly from the NMR spectra. The proposed method for studying LLE in situ can be swiftly conducted in standard chemical laboratories as medium field NMR spectrometer do not require dedicated laboratory infrastructure but enable convenient handling and fast analysis of the samples. In the present work, four non-reactive ternary solvent systems with closed miscibility gap (toluene + acetone + water, diethyl ether + acetone + water, diethyl ether + methanol + water, and acetonitrile + ethanol + cyclohexane) and one reactive ternary system (water + acetic acid + acetic anhydride) were investigated at a temperature of 22.0 °C using 1H medium field NMR spectroscopic measurements. For comparison, the composition of the coexisting phases is also examined for one non-reactive system (acetonitrile + ethanol + cyclohexane) using 13C medium field NMR spectroscopy as well as spatially resolved spectroscopy in a conventional high field NMR spectrometer. The comparison of the results of the present work to literature data shows that the new proposed method enables swift and reliable investigations of LLE.