Abstract

Efforts to understand and optimize separations employing compressible mobile phases have been limited by a lack of understanding of the mobile phase density gradient. Mobile phase compressibility leads to gradients in linear velocity and solute retention and affects separation speed and efficiency, especially in packed columns. Gas chromatography (GC), supercritical fluid chromatography (SFC), and solvating gas chromatography (SGC) each rely on compressible mobile phases. This work describes the on-column density measurement of carbon dioxide, a common carrier fluid for SFC and SGC, in packed capillary columns using Raman microspectroscopy of the position of the Fermi doublet. Correlation of the spectrum with density was calibrated over a pressure range of 15 to 290 atm at 125 and 150 °C, which then allowed for determination of the density gradient of fluid flowing through a packed capillary column. The results of this work will be used to model the flow behavior of compressible fluids to understand the effects of mobile phase compressibility on separation speed and efficiency.

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