Correction method for a concentration effect in the calculation of molecular weight averages from GPC chromatograms

TLDR: In this article, the concentration of species at each elution point was obtained from a concentration-peak height calibration curve, and molecular weight at the point was calculated by using the usual method.

Abstract: In the calculation of molecular weight averages by GPC, the traditional method uses the calibration curve obtained at the same concentration as the samples, which results in a large degree of disagreement between molecular weight averages at several concentrations. Because of the concentration dependence of peak elution position in gel permeation chromatography of polymers, correct molecular weight averages cannot be obtained if calibration concentrations are the same as sample concentrations. A computation approach which uses calibration curves at finite and zero concentrations and can correct concentration effects is shown. The concentration used varied from 0.1% up to 0.4%. The elution chromatogram was divided into several parts, and concentration of species at each elution point was obtained from a concentration–peak height calibration curve. Molecular weight at the point was obtained from a molecular weight–elution volume calibration curve corresponding to a concentration of species at the point, and molecular weight averages were calculated by using the usual method. Nearly identical values for molecular weight averages could be obtained at different concentrations, and additional support for this approach is that these values for molecular weight averages were in fair agreement with NBS data.