Abstract
Double-layer and van der Waals forces, acting between solute particles and the wall of a capillary in which an aqueous carrier solution undergoes Poiseuille flow, influence the radial distribution of particle centers. If the elution time is sufficient to allow the Brownian particles to sample all radial positions then the radial distribution is shown to be a Boltzmann one. Choosing the capillary radius so as to match the hydraulic radii of the packed column and capillary, predicted average particle residence times agreed reasonably well with all the experimental results obtained by Small (3). A parameter sensitivity study suggests that at low ionic strengths (∼10 −4 mole/liter) the average particle residence time is nearly independent of the chemical nature of the particle (i.e., Hamaker's constant and surface potential). However, at high ionic strengths (∼0.1 mole/liter) the particle's chemical nature is also important. Under the latter conditions, the secondary minimum in the particle—packing interaction energy profile becomes appreciably larger than the particle's thermal energy ( kT), causing the particles to sample the slow region near the packing surface more frequently and significantly increasing the average residence time.
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