n In the conventional
calibration (described above), there is a problem when a
sample that is chemically different from the standards used
to calibrate the column is analyzed. However, this is a
common situation; for instance, a polyethylene sample is
run by GPC while the calibration curve is constructed with
polystyrene standards. In this case, the MW obtained with
the conventional calibration is a MW related to polystyrene,
not to polyethylene. On the other hand, it is very expensive
to construct calibration curves of every polymer that
is analyzed by GPC. In order to solve this problem, a
universal calibration technique, based on the concept of
hydrodynamic volume, is used. As mentioned before, the
basic principle behind GPC/SEC is that macromolecules
are separated on the basis of their hydrodynamic radius or
volume. Therefore, in the universal calibration a relationship
is made between the hydrodynamic volume and the
retention (or, more properly, elution volume) volume, instead
of the relationship between MW and elution volume
used in the conventional calibration. The universal calibration
theory assumes that two different macromolecules
will have the same elution volume if they have the same
hydrodynamic volume when they are in the same solvent
and at the same temperature. Using this principle and
the constants K and α from the Mark-Houwink-Sakurada
equation (Eq. 17.18), it is possible to obtain the absolute
MW of an unknown polymer. The universal calibration
principle works well with linear polymers; however, it is
not applicable to branched polymers.
n In the conventionalcalibration (described above), there is a problem when asample that is chemically different from the standards usedto calibrate the column is analyzed. However, this is acommon situation; for instance, a polyethylene sample isrun by GPC while the calibration curve is constructed withpolystyrene standards. In this case, the MW obtained withthe conventional calibration is a MW related to polystyrene,not to polyethylene. On the other hand, it is very expensiveto construct calibration curves of every polymer thatis analyzed by GPC. In order to solve this problem, auniversal calibration technique, based on the concept ofhydrodynamic volume, is used. As mentioned before, thebasic principle behind GPC/SEC is that macromoleculesare separated on the basis of their hydrodynamic radius orvolume. Therefore, in the universal calibration a relationshipis made between the hydrodynamic volume and theretention (or, more properly, elution volume) volume, insteadof the relationship between MW and elution volumeused in the conventional calibration. The universal calibrationtheory assumes that two different macromoleculeswill have the same elution volume if they have the samehydrodynamic volume when they are in the same solventand at the same temperature. Using this principle andthe constants K and α from the Mark-Houwink-Sakuradaequation (Eq. 17.18), it is possible to obtain the absoluteMW of an unknown polymer. The universal calibrationprinciple works well with linear polymers; however, it isnot applicable to branched polymers.
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