Abstract

Over the past years viscous heating band broadening occurring in high pressure liquid chromatography has been studied extensively. In the present numerical study, we investigate the fine details of this band broadening contribution under extreme high-pressure conditions (2500 bar). To analyze the results, we first show that viscous heating leads to two clearly distinguishable band broadening effects, one originating from the radial differences in the species migration velocity and the other from the axial variations. It was found that the radial contribution is independent of the intrinsic band broadening of the bed (i.e. band broadening in absence of viscous heating) while it strongly depends on the radial dispersion coefficient and the retention enthalpy of the analytes. On the other hand, the axial contribution is strongly dependent on the bed intrinsic band broadening and it is found to be 4 to 5 times lower than the radial contribution. We also show the strong effect of the endfittings on the temperature gradients inside the column thus on the resulting viscous heating band broadening.

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