This investigation aimed at improving the performance of Taylor’s dispersion analysis for the fast and accurate measurement of diffusion coefficient of a minute solute in various solvents. The investigation was carried out on a capillary electrophoresis instrument by monitoring the UV absorption peak of a solute pulse and calculating the diffusion coefficient by peak efficiency. With L-phenylalanine as a main testing solute, some key factors were afterward disclosed including especially the capillary size, carrier flow velocity, injection volume and capillary conditioning. Peak tailing, large volume of sample injection and slow migration were found to underestimate the diffusion coefficient while very fast migration and high sample concentration caused overestimation. At a moderate flow velocity of 0.1―1 cm/s with a capillary of 72.44 μm I.D.×60 cm (50 cm effective) maintained at 25℃, the diffusion coefficient of aqueous L-phenylalanine was determined, giving a value of 7.02×10-6 cm2/s with error <2% and relative standard deviation <0.2% (n=3). The method was shown to be applicable to the measurement of various samples such as aqueous phenylalanine, acetone, phenol, toluene and benzene, and nonaqueous benzene (in ethanol or 1-butanol).
