Abstract
The migration behaviour of micelle counterions in micellar electrokinetic chromatography (MEKC) is treated theoretically. It is demonstrated that, due to a high degree of counterion binding, micelle counterions in commonly used surfactant systems possess negative transport numbers under MEKC conditions. This phenomenon is illustrated for a sodium dodecyl sulphate micellar system in which sodium ions possess a negative effective mobility. In addition to that, the influence of sodium and tris(hydroxymethyl)aminomethane as dodecyl sulphate counterions on the effective mobility of micelles, efficiency and selectivity in MEKC analyses is evaluated.
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