In current practice of capillary electrochromatography it is commonly
assumed that the electroosmotic flow profile in a packed column is ide
ntical to that in an open tube. However, this assumption may not be va
lid in many cases due to thermal and double layer overlap effects. In
this work, the dependence of electroosmotic mobility and plate height
upon electrolyte concentration was determined for open tubular and pac
ked column electrochromatography. As the electrolyte concentration inc
reases over the range 0.04-1 mM, the electroosmotic mobility falls off
steadily and the plate height shows a slight improvement, in the open
tube. In the packed column, by contrast, the electroosmotic mobility
is almost unchanged and the plate height improves dramatically with in
creasing electrolyte concentration. The anomalous behavior of the pack
ed column is interpreted as showing the thermal and double layer overl
ap effects, probably occurring in the densely packed segments of the c
olumn. (C) 1997 Elsevier Science B.V.