Effect of parallel segmented flow chromatography on the height equivalent to a theoretical plate II – Performances of 4.6 mm × 30 mm columns packed with 2.6 μm Accucore-C18 superficially porous particles

• Parallel segmented flow chromatography was applied to columns packed with shell particles.
• Short 4.6 mm × 30 mm columns packed with sub-3 μm particles are not radially equilibrated.
• PSFC at the column outlet improves the overall efficiency by a factor of nearly two.
• The sensitivity of weakly retained compounds increase by 25% when applying PSFC.
• Post-column band broadening should be minimized for best gradient elution performance.

The reduced trans-column (or long-range eddy dispersion) height equivalent to a theoretical plate (HETP) of short and wide 4.6 mm × 30 mm columns packed with 2.6 μm Accucore-C18 superficially porous particles was measured under conventional (no split flow) and parallel segmented (outlet and inlet) flow chromatography. The overall reduced HETP was derived from the true moments of the recorded concentration profiles. The longitudinal diffusion HETP term was measured at a very small flow rate (0.05 mL/min). The solid–liquid mass transfer resistance was derived from the shell diffusivity, using the composite Garnett–Torquato model of effective diffusion in a heterogeneous system made of a dense packing of core–shell particles immersed in a continuous matrix (the eluent). The trans-channel and short-range interchannel eddy dispersion HETP terms were assumed to be equal to the calculated h data after solving the Navier–Stokes equation and simulating the advection–diffusion transport process. Experimental results confirmed that the optimum efficiency of these short columns was increased by a factor of about two. The ratio of the detection sensitivities on the PSFC stream and on a regular stream increased from 1 to 1.45 when the retention factor decreases from about 10 to 0.5. These phenomena are due to a strong reduction of the trans-column eddy dispersion HETP term. The system loses about 60% of the sample mass when only outlet skimming is carried out when the flow rate ratio of 55% is applied, as was done in this work. It loses about 50% of the sample when inlet/outlet segmentation is applied. In gradient elution, the peak capacity is increased by only 15%, due to post-column band spreading, which should imperatively be minimized when the outlet flow is split.