Influence of modulator injection width on comprehensive two-dimensional gas chromatography peak dimensions

This study examines how the height and width of peaks exiting the secondary column of a comprehensive two-dimensional gas chromatography (GC × GC) separation are affected by the width of the pulse introduced to the secondary column. A flow-modulated GC × GC apparatus was assembled that allowed input pulse widths to be controlled precisely over a range of 10 to 70 ms. GC × GC chromatograms were obtained using secondary columns containing a polyethylene glycol stationary phase with internal diameters of 0.25 and 0.32 mm. The area, height, and width of peaks emerging from the secondary column were found to be accurately modeled by the convolution of a rectangular function with a Gaussian distribution. The rectangular function represents the input pulse, and the Gaussian distribution represents the broadening that occurs in the secondary column. The minimum peak width that could be produced by the secondary column was determined for a wide range of compounds. Injection pulse widths that matched a compound's minimum peak width produced peaks that were 25% wider than the minimum width and had heights that were 76% of the maximum possible peak height. Increasing the injection width significantly above the minimum width yielded substantially broader peaks with only a modest increase (< 25%) in peak height.