Experimental and theoretical works were performed for the separation of lar
ge polyelectrolyte such as DNA in the column packed with gel particles unde
r influence of an electric field. Since DNA quickly orients through the por
es in the field direction, this paper presents how intraparticle convection
affects the separation of DNAs in the column. Dimensionless transient mass
balance equations were derived considering diffusion and electrophoretic c
onvection. The separation criteria are theoretically studied using two diff
erent Peclet numbers in the fluid and solid phases and these criteria were
verified using two different DNAs by electrophoretic mobilities measured ex
perimentally, showing how the separation position of DNAs Varies in the col
umn according to values of Pe(f)/Pe(g) of individual DNA. Governing equatio
ns are served by an operator theory and the characteristic method to yield
the column response. (C) 2001 Elsevier Science B.V. All rights reserved.