Exact Analysis of Field-Flow Fractionation

Abstract

A rigorous convective diffusion theory is formulated for the predictive modeling of field-flow fractionation (FFF) columns used for the separation of colloidal mixtures. The theory is developed for simulating the behavior of a colloid introduced into fluid in time-dependent flow in a parallel plate channel across which a transverse field is applied. The methodology of generalized dispersion theory is used to solve the model equations. The theoretical results show that the cross-sectional average concentration of the colloid satisfies a dispersion equation with time-dependent coefficients. The results of this work, in principle, are valid for all values of time since the introduction of the colloid. It is shown that these results asymptotically approach those of the nonequilibrium theory formulated by Giddings for large values of time.

Illustrative numerical results are obtained for the case of steady laminar flow and a uniform initial distribution. The behavior of the coefficients in the dispersion equation is explained on physical grounds. Of particular interest is the fact that at large values of the transverse Peclet number P, Taylor dispersion in the FFF column is very small. Under these conditions, axial molecular diffusion as well as Taylor dispersion in the connecting tubing could make a substantial contribution to the axial dispersion observed in practical FFF columns.

The theoretical predictions are compared with the experimental data of Caldwell et al. and Kesner et al. on electrical FFF columns. The comparisons indicate that the theory has potential in predicting the performance of such systems.