Basic principles of electrolyte chemistry for microfluidic electrokinetics. Part II: Coupling between ion mobility, electrolysis, and acid–base equilibria

We present elements of electrolyte dynamics and electrochemistry relevant to microfluidic electrokinetics experiments. In Part I of this two-paper series, we presented a review and introduction to the fundamentals of acid–base chemistry. Here, we first summarize the coupling between acid–base equilibrium chemistry and electrophoretic mobilities of electrolytes, at both infinite and finite dilution. We then discuss the effects of electrode reactions on microfluidic electrokinetic experiments and derive a model for pH changes in microchip reservoirs during typical direct-current electrokinetic experiments. We present a model for the potential drop in typical microchip electrophoresis device. The latter includes finite element simulation to estimate the relative effects of channel and reservoir dimensions. Finally, we summarize effects of electrode and electrolyte characteristics on potential drop in microfluidic devices. As a whole, the discussions highlight the importance of the coupling between electromigration and electrophoresis, acid–base equilibria, and electrochemical reactions.