Relations between the separation coefficient, longitudinal displacement and peak broadening in size exclusion chromatography of macromolecules

The separation of a polymer by size exclusion chromatography is described as a series of interactions, i.e. consecutive establishments of equilibria between polymer fractions in the mobile and stationary phases followed by displacements of mobile phase containing the polymer. The elution curve is derived as the longitudinal concentration profile in the column observed in one position in space during the time of the analysis. The mean value of elution volume of a particular polymer species turns out to be the interstitial volume of the separation system divided by the mean fraction of polymer in the mobile phase. The number of the displacement–equilibrium steps can be estimated from the limiting values of the variance of the spreading function.