Abstract
Thermodynamic retention modeling to a thermally modulated comprehensive two-dimensional gas chromatography (GC × GC) system run under constant flow is performed. Significant errors in modeled second dimension retention time (tr,2) were observed, in line with past work on thermally modulated GC × GC modeling. A comprehensive study of tr,2 modeling error for alkane separations across a wide range of heating ramp rates and carrier gas flow rates was performed. Modeling errors were found to be systematic and a function of analyte elution temperature and mobile phase velocity. A model to account for these systematic errors was generated, and associated coefficients were determined which reduced average tr,2 retention time error in 144 hydrocarbon separations by an order of magnitude resulting in significant improvement in prediction accuracy. The model was used to correct the separation of 139 Grob mix analyte separations, providing an average tr,2 modeling error of 0.030 ± 0.022 s. The model successfully predicted the separation of n-alkanes on a longer second dimension column configuration.
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