Retention in reversed-phase chromatography: partition or adsorption?

Abstract

A unified framework within the hermeneutics of the solvophobic theory is employed for the treatment of experimental data with nonpolar and weakly polar substances in reversed-phase chromatography (RPC), oil–water partitioning and adsorption on activated charcoal from dilute aqueous solution. This approach sheds light on the energetic similarities between such processes driven by the hydrophobic effect. Among several stationary phase models that have been proposed in the literature for the physical representation of alkyl-silica bonded phases, the isolated solvated hydrocarbon chains model is adopted for the retention in RPC since it represents most closely the stationary phase configuration and is not based a priori on a partition or adsorption mechanism as some other models are for the retention in RPC. Using the fundamental framework of the solvophobic theory, the free energy change per unit nonpolar surface area for octanol–water and hexadecane–water partitioning, retention in RPC as well as adsorption on activated charcoal from dilute aqueous solution at 25°C are evaluated and they are found to be in good agreement with the corresponding experimental data. Furthermore, such quantities are very similar for all the above mentioned processes involving aqueous solution, in contradistinction to the predictions by the lattice theory. From the results it follows that these apparently disparate processes are subject to the same physicochemical principle. The present study demonstrates the capability of the solvophobic theory in describing the energetics of processes involving hydrophobic interactions, and exposes the difficulties in distinguishing between partition and adsorption mechanisms in RPC by using partition models based on the lattice approach. It is concluded that a clear distinction between partition and adsorption in RPC of nonpolar eluites is not apparent from thermodynamic analysis.