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Multidimensional Chromatography
                                                     Edited by Luigi Mondello, Alastair C. Lewis and Keith D. Bartle
                                                                   Copyright © 2002 John Wiley & Sons Ltd
                                                      ISBNs: 0-471-98869-3 (Hardback); 0-470-84577-5 (Electronic)


                           3 Multidimensional High Resolution
                                 Gas Chromatography



                                 A. C. LEWIS
                                 University of Leeds, Leeds, UK




                           3.1  INTRODUCTION

                           The coupling of gas chromatography columns to enable multidimensional separa-
                           tions has been widely reported in many areas of industrial and environmental analy-
                           sis. The application of multidimensional GC has been focused in essentially two
                           areas: (i) increasing peak capacity of the separation system, and (ii) increasing the
                           speed of analysis of the separation system. It was perhaps the former of these two
                           that drove the early interest in two-dimensional GC couplings, and this still remains
                           important today. Despite GC still being very much a developing technique, two-
                           dimensional systems, were being applied to the analysis of crude oil and refinery
                           products as early as the late 1960s (1). These early applications focused on achieving
                           a higher degree of deconvolution with a two-column system for the characterization
                           of feedstock and refinery fuels, and this over the past three decades has become a
                           recurring application of two-dimensional gas chromatography.
                              In common with all multidimensional separations, two-dimensional GC has a
                           requirement that target analytes are subjected to two or more mutually independent
                           separation steps and that the components remain separated until completion of the
                           overall procedure. Essentially, the effluent from a primary column is reanalysed by a
                           second column of differing stationary phase selectivity. Since often enhancing the
                           peak capacity of the analytical system is the main goal of the coupling, it is the rela-
                           tionship between the peak capacities of the individual dimensions that is crucial.
                           Giddings (2) outlined the concepts of peak capacity product and it is this function
                           that results in such powerful two-dimensional GC separations.
                              This present chapter will not focus on the statistical theory of overlapping peaks
                           and the deconvolution of complex mixtures, as this is treated in more detail in
                           Chapter 1. It is worth remembering, however, that of all the separation techniques, it
                           is gas chromatography which is generally applied to the analysis of the most com-
                           plex mixtures that are encountered. Individual columns in gas chromatography can,
                           of course, have extremely high individual peak capacities, for example, over 1000
                                   6
                           with a 10 theoretical plates column (3), but even when columns such as these are
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