Abstract

The thermophysical properties of supercritical carbon dioxide and mixtures of carbon dioxide and methanol are discussed, including their phase behavior, compressibility, and viscosity. The effects of compressibility on observed parameters such as retention factor and plate height are treated in terms of spatial and temporal averages and Giddings’ theory of nonuniform columns. Martire’s unified model for retention is used to express the local retention factor in terms of temperature and density, and the effect of modifiers on retention is briefly discussed. The sources of band spreading in supercritical fluid chromatography (SFC) are discussed, including extra-column band spreading, and the form of the van Deemter C term based on the general rate model is examined in detail. The use of kinetic plots to describe the performance of SFC separations is also described.

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