Abstract
Microemulsion electrokinetic chromatography (MEEKC) has been widely used as an indirect tool to measure octanol–water partition coefficients (logPow) of various kinds of compounds. In this paper, we present for the first time a mathematical model of the precision of logPow (ΔlogPow) as a function of the deviation of migration time (Δtm) in MEEKC, and more importantly evaluated the accuracy of the MEEKC. Our model shows that for a given microemulsion system, there is an interval of migration times, where a high precision in the determination of logPow can be obtained. However, when the migration time approaches either the migration time of the electroosmotic flow or that of the microemulsion phase, the precision of logPow deteriorates rapidly. The model was experimentally verified by the microemulsion system with migration times of 6.50 and 32.00 min for the electroosmotic flow and microemulsion phase, respectively, and we found the useful logPow interval to be 0.50–5.50. The paper also demonstrates that the calibration constants between migration times tm and predicted logPow values could be transferred with high accuracy from one MEEKC system to another as long as both systems are set up to use the same operational parameters.
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