We have developed a modified electrochromatography system which minimi
zes Joule heating at electric field strengths up to 125 V/cm. A non-li
near equilibrium model is described which incorporates electrophoretic
mobility, hydrodynamic flow velocity, and an electrically induced con
centration polarization at the surface of the stationary phase. This m
odel is able to provide useful estimates of protein retention time and
velocity in a column packed with Sephadex gel and subjected to an ele
ctric field. A correlation of electrophoretic mobility of peptide and
proteins with respect to their charge, molecular mass, and asymmetry e
nables the selection of solute target molecules for electrochromatogra
phic separations. Good separation of protein mixtures have been obtain
ed.