System zones in capillary zone electrophoresis: moving boundaries caused by freely migrating hydrogen ions

We demonstrate that system zones (SZs) can be expected in background electrolytes (BGEs) with a low buffer capacity. The mobilities of this type of SZ (m(SZ)) could be determined by calculations both based on a mathematical model and by a simulation program. The values of m(SZ) are increasing for decreasing buffer capacities and lower concentrations of the BGEs. For completely unbuffered BGEs with a pH below 7, the m(SZ) reached values up to 350x10(-9) m(2)V(-1)s(-1). This value indicates that the existence of this type of SZ originates from migrating hydrogen ions. Although both the mathematical model and simulation program do not consider the influence of the pH of the sample solution, experiments have shown that the pH of the sample solution is also very important. The lower the pH of the sample solution, the larger the m(SZ) in a specific BGE for cationic SZs. Using completely unbuffered BGEs the hydrogen ions present in the original sample start to migrate freely through the capillary tube with the mobility of a single hydrogen ion and cause stepwise disturbances in the base line of the detector trace. It is remarkable that this type of SZ appears not to affect the electromigration dispersion (EMD) in a strong way and so far only dips could be obtained experimentally.