Shedding light on mechanisms leading to convex-upward van Deemter curves on a cellulose tris(4-chloro-3-methylphenylcarbamate)-based chiral stationary phase

•Unusual convex-upward van Deemter curve observed on a polysaccharide chiral stationary phase.•Detailed investigation of kinetics and thermodynamics in chiral liquid chromatography.•Strong adsorption and absence of surface diffusion originate convex-upward van Deemter curves. An unusual convex-upward van Deemter curve was observed for the more retained enantiomer of a chiral sulfoxide (2-(benzylsulfinyl)benzamide) on a cellulose tris(4-chloro-3-methylphenylcarbamate)-based chiral stationary phase (CSP), prepared on silica particles of 1000 Å pore size. In contrast, the firstly eluted enantiomer of the same molecule exhibited the traditional convex-downward van Deemter curve. A detailed kinetic and thermodynamic investigation has revealed that this unusual phenomenon, which however has already been observed in chiral chromatography, originates when the adsorption of the compound is very strong and the solid-phase diffusion negligible. Experimentally, the intraparticle diffusion of the more retained enantiomer of the sulfoxide was found to be one order of magnitude smaller than that of the first eluted one. Overall, this translates into very little longitudinal diffusion (b-term of van Deemter curve) accompanied by high solid-liquid mass transfer resistance (c-term). Finally the comparison with another, differently-substituted chiral sulfoxide (whose enantiomers both exhibit traditional van Deemter curve behavior) has allowed to correlate these findings to the specific characteristics of the molecule.