Temperature Programming of the Second Dimension in Comprehensive Two-Dimensional Gas Chromatography

Comprehensive two-dimensional gas chromatography (GC × GC) provides a significant increase in selectivity and peak capacity for the separation of complex mixtures. Optimization of the system is often complicated, with many interconnected parameters between the two dimensions and additional problems like peak wraparound that need to be eliminated or minimized. Wraparound peaks are compounds with retention times in the second dimension that are longer than the modulation period. This results in broad peaks that elute in subsequent modulation cycles, potentially coeluting with separated compounds. The use of a secondary oven is often the solution to the problem. By applying a constant positive temperature offset from the main oven temperature, the retention of all analytes can be reduced so that they elute within their respective modulation periods. However, this reduces the separation of less retained compounds, a classical consequence of the general elution problem due to the isothermal conditions during the limited separation time in the second dimension. To overcome this problem, the second dimension was temperature-programmed by resistively heating an electrically conductive secondary column using constant current. The column was cooled through forced convection inside the GC oven within the time frame of a single modulation period. Temperature programming in the second dimension of GC × GC was able to improve separation while eliminating wraparound peaks and reducing peak widths, leading to significantly increased second dimension peak capacity.