Page 122 - Multidimensional Chromatography
P. 122

114                                     Multidimensional Chromatography

                           where this equation shows that   can be considered to be a kind of ‘saturation’ fac-
                           tor, expressing the ratio of components m to the hypothetical maximum number of
                           separable compounds  , thus expressing the degree to which the separation space is
                           saturated (8), and assuming that m     , we can replace the latter in equation (5.4),
                           thus obtaining the follow equation:

                                           P      exp(     )      exp(  )                 (5.6)

                           and consequently we can write the following:

                                                   P       exp(  )                        (5.7)

                           The dimensionless ratio P/  corresponds to the ratio between the number of visible
                           peaks, under the proposed chromatographic conditions, with the chromatographic
                           column having a peak capacity  . Differentiation of equation 5.6 with respect to
                           gives the maximum possible value of the ratio P/  and shows this to occur at     1;
                           then, the maximum ratio P/  can be estimated by the following equation:


                                               (P  ) max   exp( 1)   0.3679               (5.8)
                           which reveals that, as postulated above, the maximum number of visible peaks will
                           be equivalent to 37% of the capacity of the system peaks. Furthermore, the number
                           of single-component peaks which can be expected is given by the following:
                                                                                          (5.9)
                                                       S   mP 1

                           where m, as above in equation 5.4, is the number of components in a multicompo-
                           nents mixture and P 1 is the probability that an analyte is eluted as a single-compo-
                           nent peak, which can be expressed as follows (8):


                                           P   exp(  ) exp(  )   exp( 2 )                (5.10)
                           Consequently, the corresponding number of single-component peaks is given by the
                           following:

                                                     S m exp( 2 )                        (5.11)

                           As above, we can replace m by    and thus equation 5.11 can be rewritten as follows:

                                                   S      exp( 2 )                       (5.12)

                           which can alternatively be presented as:
                                                 S/     exp( 2 )                         (5.13)
   117   118   119   120   121   122   123   124   125   126   127