Pulsed field gradient nuclear magnetic resonance (PFG-NMR) and NMR imaging
were used to study temporal and spacial domains of an electrokinetically-dr
iven mobile phase through open and packed segments of capillaries. Characte
ristics like velocity distribution and an asymptotic dispersion are contras
ted to viscous flow behavior. We show that electroosmotic flow in microchan
nel geometries can offer a significant performance advantage over the press
ure-driven flows at comparable Peclet numbers, indicating that velocity ext
remes in the pore space of open tubes and packed beds are drastically reduc
ed. An inherent problem of capillary electrochromatography that we finally
address is the existence of wall effects when in the general case the surfa
ce zeta-potentials of the capillary inner wall and the adsorbent particles
are different. Using dynamic NMR microscopy we were able resolve this syste
matic velocity inequality of the flow pattern which strongly influences axi
al dispersion and may be responsible for long time-tails of velocity distri
bution in the mobile phase. (C) 2001 Elsevier Science Inc. All rights reser
ved.