Electrokinetic flow and electric conduction of salt-free solutions in a capillary

The electrokinetic flow and accompanied electric conduction of a salt-free solution in the axial direction of a charged circular capillary are analyzed. No assumptions are made about the surface charge density (or surface potential) and electrokinetic radius of the capillary, which are interrelated. The Poisson–Boltzmann equation and modified Navier–Stokes equation are solved for the electrostatic potential distribution and fluid velocity profile, respectively. Closed-form formulas for the electroosmotic mobility and electric conductivity in the capillary are derived in terms of the surface charge density. The relative surface potential, electroosmotic mobility, and electric conductivity are monotonic increasing functions of the surface charge density and electrokinetic radius. However, the rises of the relative surface potential and electroosmotic mobility with an increase in the surface charge density are suppressed substantially when it is high due to the effect of counterion condensation. The analytical prediction that the electroosmotic mobility grows with increases in the surface charge density and electrokinetic radius agrees with the experimental results for salt-free solutions in circular microchannels in the literature.