Gel permeation chromatography of polymer mixtures

When mixtures of polymers are analyzed in a common gel permeation chromatographic solvent the peak elution volumes of both components are shifted with respect to their values at their nominal concentrations in the same solvent and column set. In this article a theory which has been applied previously to account for concentration effects of a single polymer in a GPC solvent is modified to predict peak elution volumes in polymer mixtures. The model invokes solvent‐solute interactions only and provides quantitative predictions of the behavior of mixtures of anionic polystyrene samples with other polystyrenes and with polybutadienes. There is no indication of polymer‐polymer repulsive effects except for polystyrene‐poly(methylmethacrylate) mixtures at relatively high concentrations.