A method of calculating the second dimension hold-up time for comprehensive two-dimensional gas chromatography

A method of calculating the second dimension hold-up time for comprehensive two-dimensional gas chromatographic (GC × GC) data was developed by incorporating the temperature information of the second dimension column into the calculation model. The model was developed by investigating the relationship between the coefficients in each of six literature reported nonlinear models and the relationship between each coefficient and the second dimension column temperature. The most robust nonlinear function was selected and further used to construct the new model for calculation of the second dimension retention time, in which the coefficients that have significant correlation with the column temperature are replaced with expressions of column temperature. An advantage of the proposed equation is that eight parameters could explain the second dimension hold-up time as well as retention time corresponding to n-alkanes and column temperature in the entire chromatographic region, including the chromatographic region not bounded by the retention times of n-alkanes. To optimize the experimental design for collecting the isothermal data of n-alkanes to create the second dimension hold-up time model, the column temperature difference and the number of isothermal experiments should be considered simultaneously. It was concluded that a total of 5 or 6 isothermal experiments with temperature difference of 40 or 50 °C are enough to generate an accurate model. The test mean squared error (MSE) of those conditions ranges from 0.0428 to 0.0532 for calculation of the second dimension hold-up time for GC × GC data.

► A novel model for calculation of the second dimensional hold-up time in GC × GC.
► The model explains second hold-up time related to all column temperatures.
► It outperformed the literature reported methods in terms of prediction accuracy.
► Optimal experimental design was investigated to efficiently create the model.