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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)


                           4 Orthogonal GC–GC


                                 P. J. MARRIOTT
                                 Royal Melbourne Institute of Technology, Melbourne, Australia




                           4.1  INTRODUCTION TO MULTIDIMENSIONAL
                           GAS CHROMATOGRAPHY
                           A multidimensional gas chromatography (MDGC) separation involves two columns
                           in the separation process. However, simply the joining together of two columns is
                           not sufficient to produce the MDGC process. The direct coupling of two different
                           columns– called multichromatography (1) – is able to improve separation, but is
                           essentially the same as mixing stationary phases (in this case, the two phases on the
                           coupled columns) to obtain an improved selectivity in the separation. In Figure 4.1,
                           the interface or valve at the confluence of the two columns is simply a column join in
                           this instance. There is no increase in capacity (total number of available separation
                           plates) in the system, but merely a shifting of the peak relative retentions. This exper-
                           iment has been improved in its implementation by locating a valve between the two
                           columns, thus allowing the mid-point pressure to be altered (the stimulus for the
                           valve in Figure 4.1 is variable pressure). This is termed a pressure-tuning experiment
                           (2), and by varying the pressure the relative contribution of each column to the sepa-
                           ration can be varied, and so a wide range of apparent retention factors can be
                           obtained. By optimization of the pressure and other experimental settings (3, 4), the
                           chromatographic separation can be consequently optimized according to the mixture
                           being studied. This method still does not qualify to be called MDGC. The MDGC
                           definition must be cast to allow differentiation between the accepted MDGC experi-
                           ment and the above coupled-column approaches. It must incorporate the process of
                           isolation of zones of effluent from column 1 (also called dimension 1 (1D)) and then
                           passing them to column 2 (also called dimension 2 (2D)). One could believe that this
                           must involve extra-column couplings, but that has been obviated by recent develop-
                           ments (see below). Thus, the simplest MDGC arrangement will be to use a valve
                           switching system that can pass zones of effluent from 1D to 2D. This will be the sub-
                           ject of other chapters in this book and so will not be treated any further here. In the
                           case of the system shown in Figure 4.1, the interface or valve will be a mechanical
                           valve or a pressure switching valve that can be switched to pass effluent from 1D to
                           2D, while the stimulus will be the electronic valve drive or balancing pressure sup-
                           ply. Those zones not passed to 2D will be directed to the detector at the end of 1D.
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