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Handbook of Size Exclusion Chromatography and Related ...

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2.1 Molecular Weight Grades <strong>of</strong> PVP Based on KValue<br />

The molecular weights <strong>of</strong> PVP have traditionally been characterized by the<br />

Fikentscher(2)Kvalue,whichisrelatedtorelativeviscositymeasuredat258Cby<br />

loghrel C ¼<br />

75K2 0<br />

1þ1:5K0C þK0<br />

where K¼1000 K0 <strong>and</strong> Cis the solution concentration in g/dL. An increase<br />

inh relcorrespondswithanincreaseinKvalue.Table1showsthedependence<strong>of</strong>K<br />

valueonh relforgivenvalues<strong>of</strong>relativeviscosity,measuredat1g/dL(or1%wt/<br />

vol). As seen from Table 1, aPVP polymer with arelative viscosity <strong>of</strong> 2would<br />

have aKvalue <strong>of</strong> 60 <strong>and</strong> the polymer would be referred to as aK-60. In industry,<br />

the K value is generally obtained from a table similar to Table 1, with<br />

concentrations specified by the U.S. Pharmacopoea (USP) for the different<br />

molecular weight grades <strong>of</strong> PVP.The USP specifies that K-30, K-60, or K-90<br />

should be obtained from 1% solutions <strong>and</strong> K-15 <strong>and</strong> K-120 should be obtained<br />

from 5<strong>and</strong> 0.1% solutions, respectively.<br />

The molecular weight ranges <strong>of</strong> various commercial Kvalue grades <strong>of</strong> PVP<br />

areshowninTable2.The M w<strong>of</strong>anunknownPVPsample canbecalculatedfrom<br />

intrinsic viscosity if the Mark–Houwink equation, which correlates intrinsic<br />

viscosity with Mw is known from the literature. The unknown PVP sample should<br />

be similar in branching <strong>and</strong> polydispersity to the PVP samples from which the<br />

Mark–Houwink equation is derived. Levy <strong>and</strong> Frank published the following<br />

Mark–Houwink equation in 1955 (3) for unfractionated PVP samples in water at<br />

. Senak et al. published the following Mark–<br />

258C: [h] ¼ 5:65 10 2 M 0:55<br />

w<br />

Houwink equation in 1987 (4) for unfractionated PVP samples in water–methanol<br />

(1:1 vol/vol) with 0.1 M LiNO3 at 258C: [h] ¼ 1:32 10 4 M 0:65<br />

w .<br />

Table 1 K Value vs. Relative Viscosity at 1% Concentration (wt/vol)<br />

K value<br />

Relative<br />

viscosity K value<br />

Relative<br />

viscosity<br />

20 1.120 60 2.031<br />

25 1.175 65 2.258<br />

30 1.243 70 2.527<br />

35 1.325 75 2.846<br />

40 1.423 80 3.225<br />

45 1.539 85 3.678<br />

50 1.677 90 4.219<br />

55 1.839 95 4.870<br />

© 2004 by Marcel Dekker, Inc.

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