Chromatographic adhesion law to simplify surface energy calculation

• We established chromatographic adhesion law (Kia=eΔEia/kT).
• We derived an equation to calculate the dead retention time (t0=(trcn+2trcn−(trcn+1)2)/(trcn+2+trcn−2trcn+1))(t0=(trcn+2trcn−(trcn+1)2)/(trcn+2+trcn−2trcn+1)).
• Literature n-alkanes’ parameters vary the calculated surface components.
• Literature n-alkanes’ parameters should be regressed to entire linearity.

The calculated data of inverse gas chromatography (IGC) vary depending on the calculation methods and the n-alkane series. To overcome IGC data variability, this paper combines the Van Oss–Good–Chaudhury concept, the Dorris–Gray equation, the Schultz equation, the Fowkes equation and group contribution theory to establish the chromatographic adhesion law and its equation is Kia=eΔEia/kT. In the equation, Kia is the adhesion retention factor of a chemical group, ΔEia represents the increased chromatographic adhesion energy due to this group and kT   expresses the thermal kinetic energy of the molecule containing this group. The dispersive component (γSd), the electron acceptor component (γS+) and the electron donor component (γS−) of a solid surface are then calculated from ΔEia. Through correlating the retention time with the adhesion energy, this law expresses mathematically the chromatographic adhesion phenomenon of IGC at the infinite dilution region. This paper also derives a new equation to calculate the retention time of a non-adsorbing probe (dead retention time).