Polyelectrolytes as secondary calibration standards for aqueous size‐exclusion chromatography

Abstract The effect of the ionic strength of the solvent on the size‐exclusion chromatography of narrow molecular weight dextrans and monodisperse sodium polystyrene sulfonates has been investigated. In both NaOH and NaCl solutions the elution volume of the sodium polystyrene sulfonates increased as the ionic strength was increased, while the elution volume of the dextrans decreased slightly as the ionic strength was increased. The elution data for various ionic strength solvents could not be described by the traditional universal calibration procedure of plotting the product of the intrinsic viscosity and the molecular weight vs. the elution volume. By using a modified calibration procedure which includes excluded volume effects, the elution data can be described for NaOH solution of moderate and high ionic strength. This modified calibration technique was unable to describe the elution data for very low ionic strength NaOH solutions and for the NaCl solutions. Possible explanations of the inability of straightforward size exclusion chromatographic calibration techniques to quantitatively described all the observed elution behavior are discussed.