The applicability of electrically driven (ED) size-exclusion chromatography
for the separation of synthetic polymers was investigated in capillary col
umns packed with 5 mu m particles with different pore sizes using dimethylf
ormamide as the mobile phase. It was found that under ED conditions a signi
ficant intraparticle pore flow was generated. The relative intraparticle ve
locity with respect to the average interparticle velocity increased with th
e pore size and ionic strength. It was also observed that with increasing p
ore flow the plate height of polymers decreased considerably. On the other
hand, the intraparticle velocity impaired the selectivity of the separation
. In some cases the loss in selectivity was so large that hardly any separa
tion of polymers was achieved. The effect of pore flow on the retention of
polymers in porous particles could be described well with a simple theory.
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