Effect of the polydispersity on the dispersion of polymers through silicas having different morphologies (fully...

The effect of the polydispersity of polystyrenes on the dispersion through silicas having different morphologies (fully porous, core-shell particles and monoliths) was investigated. The heights equivalent to a theoretical plate (HETP) of those columns were measured for a small molecule (toluene) and a series of polystyrenes of different sizes in non-adsorbing conditions. The different contributions to the total HETP including polydispersity were determined experimentally. The longitudinal diffusion and the mass transfer resistance term were obtained from peak parking experiments. The eddy dispersion was obtained from models and experiments. The effect of polydispersity on the HETP values (H_poly) can thus be calculated from the total HETP by substraction of the other contributions. The results were compared to the Knox model which surestimates the H_poly values for porous and core-shell particles which is usually explained by an overestimation of the polydispersity index (PDI) given by the manufacturer. The PDI of two polymers (P02, M_w= 690 g.mol^-1 and P03, M_w=1380 g.mol^-1) was verified by liquid chromatography by separating each fraction of the polymer on the silica columns by using adsorbing conditions which are obtained with a mixture of heptane and THF. The PDI obtained are comparable to the PDI given by the manufacturer meaning that the assumptions made by Knox are not entirely valid. A direct method is proposed in this paper in order to determine H_poly. In this method the excess of spreading as compared with a polymer with only one size corresponding to the average size is studied assuming the polymer size distribution is gaussian. The H_poly values obtained by the direct method are comparable to the experimental values.