Retention modeling and retention time prediction in gas chromatography and flow-modulation comprehensive two-dimensional gas chromatography: The contribution of pressure on solute partition

•The effects of pressure of solute partition and retention in GC.•Improvement of predicted retention time accuracy considering pressure contribution.•The relevance of considering pressure in GC and FM-GCxGC.•A new method for stationary phase film thickness determination.•The accuracy of gas velocity calculation in the two columns in FM-GCxGC.

This study aims at modelling and predicting solute retention in capillary Gas Chromatography (GC) and Flow Modulation comprehensive GC (FM-GCxGC). A new thermodynamic model, taking into account the effects of temperature and pressure, is proposed to describe the variation of the equilibrium partition constant of a solute during its elution. This retention model was challenged with the classical one, and both were applied to: (i) stationary phase film thickness indirect estimation; (ii) retention time (RT) prediction of a set of 11 model polycyclic aromatic hydrocarbons (PAHs) on the SLB-IL60 and DB-35MS columns, in temperature-programmed mode. Film thickness determination led to values about 2 times lower than those indicated by column nominal dimensions, whatever the employed model. Prediction of retention times in GC led to 0.84 and 0.26% mean errors using the classical and the extended models, respectively. Prediction in GCxGC gave 5.5 and 0.44% mean errors in 1st dimension RTs, and 7.3 and 2.2% mean errors in 2nd dimension RTs, using the classical and the extended models, respectively.