Effect of multivalent ions on electroosmotic flow in micro- and nanochannels.

In this work, the effect of multivalent ions on electroosmotic flow is investigated for multiple electrolyte components. The cases studied include incorporating Ca2+ and HPO4(2-) and other monovalent ions, such as K+ and H2PO4-, into an aqueous NaCl solution. The governing equations are derived and solved numerically. The boundary conditions for the governing equations are obtained from the electrochemical equilibrium requirements. In comparison with monovalent ions, the results show that in micro- and nanochannels having fixed surface charges, multivalent counterions, even in very small amounts, reduce electroosmotic flow significantly, while the multivalent co-ions have little effect on the electroosmotic flow. Due to the enhanced ion-wall interactions multivalent counterions compose the majority of ions in the electric double layer (EDL), causing a decrease of net charge at the surface.