Molecular and Continuum Transport Perspectives on Electroosmotic Slip Flows

Velocity slip in electroosmotic flows (EOF) is investigated using an analytical solution of Poisson–Boltzmann and Stokes (PB-S) equations with slip correction, and the results are compared with the predictions from molecular dynamics (MD) simulations. Particularly, EOFs of NaCl solution in silicon nanochannels are simulated, and channel dimensions are picked to exhibit plug flow behavior in the bulk region. Electrochemical conditions are specified within the validity region of PB theory to avoid charge inversion and flow reversal effects. The analytical model shows normalization of the slip length (an interfacial property) with the Debye length determined by the ionic concentration, implying that the slip enhancement in EOFs is independent of the channel height. MD results are compared with the analytical solution using the apparent viscosity and slip lengths determined by force-driven flow simulations in charged silicon nanochannels. Onset of slip velocity within the electrical double layer and its effects on EOF are investigated as a function of the liquid–wall interaction strength. Good agreements between the analytical solutions and MD results validate PB-S equations in nanochannels as small as 3.5 nm. Results validate that slip enhancement in EOFs is independent of the channel height, which constitutes a theoretical basis for the slip-length measurements on hydrophobic dielectric surfaces using EOFs.