Errors involved in the existing B-term expressions for the longitudinal diffusion in fully porous chromatographic...

Peak parking experiments have been performed on three RP-HPLC different columns, using two different components and a variable mobile phase composition. The aim of the study was to investigate whether the B-term diffusion expressions currently used in the literature (which are all Knox-type models) should be replaced by the effective diffusion expressions that have been developed in the frame of the effective medium theory (EMT). Although the EMT-expressions are not fully accurate either (the mathematics of the complex interactions between different diffusion zones that are in close contact are too demanding to catch them in an exact analytical expression), they at least are physically sound and do not violate Maxwell's basic law of diffusion. Further they also provide a much better approximation of the numerically calculated effective diffusivity in the theoretical test situation considered in part I. The present study shows that the values of the surface or stationary phase diffusion coefficient that are derived from peak parking models can depend heavily on the employed B-term model. The EMT-based B-term expressions lead to values of the surface diffusion coefficient that vary much less strongly with the phase retention factor than if one of the Knox-type models is used to analyze the data. This implies that, since all peak parking experiments that have been performed in the past have all been interpreted with a Knox-type model, the conclusions that have been drawn from these studies should all be moderated or at least revisited.