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52   I / CHROMATOGRAPHY/ Derivatization


           different from that of the high performance
           layers; the primary virtue of the latter is that a shorter
           migration distance is required to achieve a given ef-
           Rciency, resulting in faster separations and more com-
           pact zones that are easier to detect by scanning den-
           sitometry. The minimum in the average plate height
           under capillary-controlled conditions is always
           greater than the minimum observed for forced-Sow
           development, indicating that under capillary-control-
           led Sow conditions the optimum potential perfor-
           mance is currently never realized in full. Under for-
           ced-Sow conditions the minimum in the plate height
           is both higher and moved to a lower velocity
           compared with values anticipated for a column in LC,
           (Figure 13). Also, at increasing values of the mobile-
           phase velocity, the plate height for the layer increases
           more rapidly than is observed for a column. At the
           higher mobile-phase velocities obtainable by forced-
           Sow development, resistance to mass transfer is an
           order of magnitude more signiRcant for layers than
           for columns. The large value for resistance to mass
           transfer for the layers may be due to restricted dif-
           fusion within the porous particles or is a product of
           heterogeneous kinetic sorption on the sorbent and the
           binder added to layers to stabilize their structure. The
           consequences for forced-Sow TLC are that separ-
           ations will be slower than for columns and fast separ-
           ations at high Sow rates will be much less efR-















                                                           Figure 14 Separation of polycyclic aromatic hydrocarbons by
                                                           forced-flow TLC with online detection (elution mode). A silica gel
                                                           high performance layer, migration distance 18 cm, with hexane as
                                                                                 1
                                                           the mobile phase (0.07 cm s  ) was used for the separation.
                                                           (Reproduced with permission from Poole CF and Poole SK (1994)
                                                           Analytical Chemistry 66: 27A, copyright ^ American Chemical
                                                           Society).
                                                           cient than for columns, although in terms of total
                                                           efRciency and separation speed the possibilities
                                                           for forced-Sow development are signiRcantly better
                                                           than  those  of  capillary-controlled  separations
           Figure 13 Plot of the reduced plate height (H/d P ) against the  (Figure 14).
           reduced mobile-phase velocity (ud P /D M ) for a high performance
           and a conventional TLC layer using forced-flow development
           superimposed on a curve for an ideal LC column. (Reproduced Separation Quality
           with permission from Fernando WPN and Poole CF (1991) Jour-
           nal of Planar Chromatography 4: 278, copyright ^ Research  The general object of a chromatographic separation
           Institute for Medicinal Plants.)                is to obtain an acceptable separation (resolution)
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