Reduced sample recovery is a frequent feature of liquid chromatography of macromolecules under critical conditions of enthalpic interactions, LC CC. Several methods of assessment of LC CC sample recovery are compared. A novel approach is based on an online combination of the LC CC column with a non‐interactive SEC column. It provides not only the amount but also the molar mass of the eluted/withheld polymer. The procedure was tested with poly(methyl methacrylate)s, bare silica gel column packings and “critical eluent” tetrahydrofuran/toluene. It was shown that macromolecules with higher molar masses were preferentially trapped within the LC CC column packing so that the eluted part of the sample was no longer representative. The incomplete polymer elution can make the LC CC polymer analyses susceptible to significant experimental errors.
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