A mathematical model describing electrokinetically driven mass transport phenomena in microfabricated chip devices is presented in this paper. The model accounts for principal material transport mechanisms such as electrokinetic migration (electrophoresis and electroosmosis) and diffusion. A computer code that implements the model is capable of simulating transport of materials during electrokinetic manipulation in 2-D channel structures. The computer code allows arbitrary channel geometries with various boundary conditions for the electric field and the sample concentration. Two fundamental microfluidic chip elements, a cross and a mixing tee, are of particular interest. An electrokinetic focusing experiment using a cross structure and mixing in a tee structure are simulated. Simulations revealed an optimum focusing voltage for which the ratio of sample concentration to sample width is maximized. They also verified that the mixing tee provides very accurate dilution/mixing characteristics for both charged and neutral samples. Good agreement between simulated and experimental data verified the accuracy of the mathematical model.

Computer simulations are used to study electrokinetic injections on microfluidic devices (microchips). The gated and pinched injection techniques are considered. Each injection technique uses a unique sequence of steps with different electric field distributions and field magnitudes in the channels to effectuate a virtual valve. The goal of these computer simulations is to identify operating parameters providing optimal valve performance. In the pinched injection, the conditions of both loading and dispensing steps were analyzed to reach a compromise between the sample plug spatial extent and its concentration. For the gated injection, the condition of leakage free valve operation was found for the sample loading step. The simulation results for the gated valve are compared with experimental data.

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The evolution of an isotachophoresis (ITP) system in acidic or basic pH ranges can be quite different from that predicted by the existing theory. It was found theoretically and proved experimentally that the contribution of hydrogen or hydroxyl ion to conductivity of solution and/or its net charge changes the behavior of the ITP system, creating in the terminating electrolyte an additional zone close to the initial interfaces between electrolytes (leader and terminator). One boundary of the zone, being either sharp or dispersed, moves toward the leader; the other is always sharp and stationary and coincides with initial electrolytes' discontinuity. The latter can be registered in the presence of electroosmotic flow which delivers it to the detection point. In order to describe the dynamics of the ITP system at pH extremes an algorithm of analytical solution was developed, based on the revised Kohlrausch theory. Its predictions coincide well with computer simulations and experimental data. The results presented can help in a correct analysis of ITP data and explain some confusing phenomena which were considered to be artifacts.

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Transient states in the evolution of electrophoretic systems comprising aqueous solutions of weak monovalent acids and bases are simulated. The mathematical model is based on the system of nonstationary partial differential equations, expressing the mass and charge conservation laws while assuming local chemical equilibrium. It was implemented using a high resolution finite-difference algorithm, which correctly predicted the behavior of the concentration, pH and conductivity fields at low computational expense. Both the regular and the irregular modes of separation in capillary zone electrophoresis and isotachophoresis are considered. It is shown that the results of separation, particularly zone order, strongly depend on pH distribution. Simulation data as well as simple analytical assessments may help to predict and correctly interpret the experimental results.