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Sepsci*21*TSK*Venkatachala=BG
                                                                                I / CHROMATOGRAPHY    51


                                                           broadening resulting from radial temperature gradi-
                                                           ents. Separations in MEKC are typically carried out
                                                           with between 100 000 and 500 000 theoretical
                                                           plates. Adsorption of solutes on the column wall can
                                                           greatly reduce the potential column efRciency
                                                           and experimental conditions should be optimized to
                                                           minimize these contributions whenever possible.
                                                           Planar Chromatography
                                                           The consequence of the suboptimal mobile-phase
                                                           velocity in planar chromatography obtained by capil-
                                                           lary-controlled Sow is that zone broadening is domin-
                                                           ated by diffusion. Since the mobile-phase velocity
                                                           varies approximately quadratically with migration
                                                           distance, solutes are forced to migrate through regions
                                                           of different local efRciency and the plate height
                                                           for the layer must be expressed by an average value
                                                           (Figure 12). Each solute in the chromatogram experi-
                                                           ences only those theoretical plates over which it mi-
           Figure 11 Separation of aromatic compounds by CEC on
                                                           grates, with solutes close to the sample application
           a50 cm 50  m i.d. fused silica capillary column packed with
           1.5  m spherical octadecylsiloxane-bonded silica gel with 70%  point experiencing very few theoretical plates and
           (v/v) acetonitrile buffer as mobile phase, temperature 253C, and  those close to the solvent front experiencing up to an
           field strength 30 kV.
                                                           upper limit of about 5000. High performance layers,
                                                           with a nominal average particle size of about 5  m,
           of micelle sizes. Resistance to mass transfer in the  provide more compact zones than coarser particles,
           mobile phase is minimized by the capillary dimen-  provided that the solvent front migration distance
           sions of the column and the small size and homogene-  does not exceed about 5}6 cm; beyond this point
           ous distribution of the micelles throughout the mobile  zone broadening exceeds the rate of zone centre
           phase combined with the near-perfect plug Sow of the  separation. When the development length is opti-
           mobile phase. Thermal dispersion, as described for  mized the separation performance of conventional
           CEC, is an additional potential source of zone  layers (average particle size about 10  m) is not very
































           Figure 12 Variation of the average plate height as a function of the solvent front migration distance for conventional and high
           performance silica gel layers with capillary-controlled and forced-flow development. (Reproduced with permission from Poole CF and
           Poole SK (1997) Journal of Chromatography A 703: 573, copyright ^ Elsevier Science B.V.)
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