Pressure, temperature and density drops along supercritical fluid chromatography columns. II. Theoretical simulation for neat carbon dioxide and columns packed with 3-μm particles

When chromatography is carried out with high-density carbon dioxide as the mobile phase, the required pressure gradient along the column is moderate but this mobile phase is highly compressible so, under certain experimental conditions, its density may decrease significantly along the column. Such an expansion absorbs heat and causes cooling of the column. The resulting heat transfer causes the formation of axial and radial gradients of temperature and density that may become large under certain conditions. In the first part of this series the pressure, temperature, and density drops were measured over a wide range of experimental temperature and pressure conditions, along columns packed with 3- and 5-μm particles. These columns were suspended in a circulating air bath and were either bare or covered with foam insulation. The behavior of these columns was discussed with special attention to their thermal heterogeneity. In this part we scrutinize the application of two heat transfer models to predict the pressure, temperature and density drops. One is a two-dimensional model that takes into account the axial and radial variations of the relevant chromatographic parameters along the column. The other, one-dimensional model ignores the radial variations of these parameters. The numerical solutions of the two-dimensional model are in excellent agreement with independent experimental data. The one-dimensional model can also be applied for the analysis of the behavior of supercritical fluid chromatography (SFC) columns away from the critical conditions.

► We measured pressure, temperature, and density drops in SFC columns.
► We present a two-dimensional model (I) and one-dimensional model (II) of these drops.
► Numerical solutions of model I agree with experimental data.
► Model II can be applied for modeling of SFC away from the critical conditions.