Concentration effects in gel‐permeation chromatography

Rudin, Alfred

doi:10.1002/pol.1971.150090914

Cited by 70 publications

(21 citation statements)

References 28 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The Rudin model 13 and an earlier, semiempirical version 11 (18) where F is the volume fraction of suspended material and is equal, in general, to (19) In the limit of infinite dilution, eq 5, 18, and 19 are equivalent to…”

Section: Concentration Dependence Ofgpc Elution Volumesmentioning

confidence: 99%

“…This author was able to predict the elution behavior with a theory based in part on Rudin's earlier model. 11 We have fitted the experimental data to the two parameter linear equation 23 to obtain an expression for the universal calibration curve in terms of v. and M [17]. The effects of concentration for a given polystyrene follow from eq 23 of the Yamakawa model or from eq 24 for the Rudin version The results are presented graphically in Figure 6, where it can be seen that neither model can be distinguished experimentally.…”

Section: Prediction Of Gpc Column Behaviormentioning

confidence: 99%

“…A semi-empirical model has been discussed which can be used to correct for concentration effects in GPC. 11 This model has also been applied to universal calibration in GPC. 12 The theory did not fit experimental observations in theta solvents and a revision (herein-after referred to as the Rudin model) has been published which is less empirical and which appears to fit the elution behavior of polymers in all * On leave from Chemical Engineering Department, Arya-Mehr University of Technology, Tehran, Iran.…”

mentioning

confidence: 99%

“…Here is a parameter given by and Z is the so-called interaction parameter, which is related to ao by ao 2 =0.541 +0.459(1 +6.04Z) 0 ' 46 (11) It is evident from eq 11 that the limiting value of Z is zero as the polymer solution approaches theta conditions. Introduction of eq 2, 7, and 9 and the value of ¢' into eq 1 yields 8 first yields a 0 and insertion of this value into eq 11 permits evaluation of the interaction parameter Z.…”

mentioning

confidence: 99%

“…That is to say, concentration effects are more pronounced with higher molecular polymers and in good solvents. 11 The critical concentration Cx, which is defined as the concentration at which the dimensions of the solvated macromolecules have been reduced to their theta condition values, can be estimated by substituting a=1 into eq 9 lna0 (14)…”

mentioning

confidence: 99%

See 4 more Smart Citations

Effect of Solvent on Concentration Dependence of Hydrodynamic Volumes and GPC Elution Volumes

Mahabadi

Rudin

1979

Polym J

Self Cite

View full text Add to dashboard Cite

ABSTRACT:The models of Yamakawa and Rudin were used to predict the effects of polymer concentration on hydrodynamic volumes of solvated macromolecules and on peak elution volumes in gel-permeation chromatographic (GPC) analyses. Both theories predict GPC behavior accurately for all systems of practical analytical interest. Yamakawa theory calculations predict that a concentration region may exist in which the polymer hydrodynamic volume may be greater in a poorer solvent than in a thermodynamically better solvent. This "cross-over" is noticeable for high molecular weight polymers at relatively high concentrations which are beyond the dilute region for which the theory was developed. Some GPC observations with porous glass packings are nevertheless in qualitative agreement with this prediction. Both models account for the effects of concentration, solvent choice, and polymer molecular weight on GPC column behavior.KEY WORDS Hydrodynamic Volume I Elution Volume I GPC I Gyration Radius I It is well known that the peak elution volume tends to increase with increasing concentration of a given polymer in the feed to GPC column sets. 1 -10 The concentration effect is more pronounced with polymers of narrow molecular weight distribution and higher mean molecular weight. The effect of concentration decreases as the thermodynamic quality of the GPC solvent deteriorates and is practically non-existent in theta mixtures.The concentration effect in GPC was explained as a consequence of the reduction of the effective hydrodynamic volume of solvated polymer coils with increasing concentration. A semi-empirical model has been discussed which can be used to correct for concentration effects in GPC. 11 This model has also been applied to universal calibration in GPC. 12 The theory did not fit experimental observations in theta solvents and a revision (herein-after referred to as the Rudin model) has been published which is less empirical and which appears to fit the elution behavior of polymers in all * On leave from Chemical Engineering Department, Arya-Mehr University of Technology, Tehran, Iran. GPC solvents. 9 ' 13 -16 The Rudin model seems to be the only one which has been used quantitatively to correct GPC data for concentration effects. It was of interest, therefore, to determine whether a model which is accepted as more "orthodox" in current polymer solution theory would also be applicable to this practical problem. In this article, we compare the Rudin model 13 with Yamakawa's 17 theory relating the concentration and effective hydrodynamic volume of solvated polymers. It will be shown that the two theories yield equivalent predictions under almost all conditions which are likely to be encountered in GPC analyses. The two deviate only in the case of very high molecular weight polymers at relatively high concentrations in very good solvents. The Rudin model is more convenient to use. The Yamakawa theory predicts that the dimensions of a high molecular weight polymer coil in a good solvent may be smaller than those in a...

show abstract

Section: Concentration Dependence Ofgpc Elution Volumesmentioning

confidence: 99%

Section: Prediction Of Gpc Column Behaviormentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

Effect of Solvent on Concentration Dependence of Hydrodynamic Volumes and GPC Elution Volumes

Mahabadi

Rudin

1979

Polym J

Self Cite

View full text Add to dashboard Cite

show abstract

Beiträge zur gelchromatographischen Fraktionierung im präparativen Maßstab. II. Zum Einfluß der Gelanordnung auf das Elutionsverhalten und die Trennqualität

Albrecht

Glöckner

1980

Acta Polymerica

View full text Add to dashboard Cite

Ausgehend von einer Analyse des Einflusses der Gelanorduung auf die Trennqualitat bei praparativ-gelchromattrgraphischen Fraktionierungen werden Ergebnisse zum Elutionsverhalten und zur Differenzierfahigkeit bei unterschiedlicheu Gelanordnungen mitgeteilt,. Die Iintersuchung zeigte, dalJ bei der praparativen GPC neben geeigneten Tragern die Gelanordnung entscheidend die erreichbare Trenneffektivitat und damit den erforderlichen Fraktionieraufwand beeinflufit. Die Ursache hierfiir ist in koiizentratiolishedingten Veriinderungen des gelchromatographisrh~~n Trennprozesses zu sehen. MccJtedosafiua no $pa?cyuonuposanuroAerno8oa npenapamusnoii aenb-xpowamozpa$uu. I I . 0 sJtumuu pacnonoxcetmfi cmes rta nosedeMue n p u a~ttouposanuu u a$$ie~rnu~nocrnb pa313enenuz L~X O~F I 113 aaanma BJIHFIHAFI pacnonoxeHm emoeB Ha ~@ @~K T H B H O C T~ pasneneam n p~ @paKiinompoBamm a Tamie 06 ~@ @~K T H B H O C T H p a 3~e n e~m B cnyqae P~B J I A~H~I X paenonowemti renefi B C~O F I X . klccne~osawm noKa3am11, w o ~aprxny c npmronHocTbm Hocarenei paenonoweme renei B CJIOFIX peuramqm 06pa30M onpe,qenxeT IIpmmiaM~ 3~0 r o RRJIFIIOTCFI ~~B H C F I~P I~ OT RoHqewrpatim nmeifemfi R npouecce renb-xpoMaTorpa~nserKoro p a 3~e n e~m~.Contributions to the gel ckrornatograph ic fraAonation on preparative scale. I I . The effect of gel arrangetneni on the elfttion behaviour and the separation quality Rased on the determination of the effect of gel arrangement on the separation quality in preparative gelchromatographic separation the results on the elution behaviour and differentiation ability of different gel arrangements are described. Besides suitable carriers the gel arrangement was found to affect decisively the separation activity and thus the efficiency of fractionation. This is obviously caused hy concentration-dependent changes of the gelchromatographic scparation proct'ss.MeTOAOM IIpeIIapaTEBHOfi rnx IIPHBORFITCFI 3KCrIePLIMeIITaJIbMLie HaHHbIe 0 IIOBeReH1111 re.TIefi npll 3JIIO11pORaHHI<, XOCTPIFaeMJ'H, 3@@eKTKBAOCTb pa3AeJIeH1153 11 TeM CaMLIM HeO6XOARMYlO TPj'~OeMEOCTL npG1 @paKI~~~H11pORaH1111.

show abstract

Effect of solute concentration on hindered diffusion in porous membranes

Shao

Baltus

2000

AIChE Journal

View full text Add to dashboard Cite

Concentration effects in gel‐permeation chromatography

Cited by 70 publications

References 28 publications

Effect of Solvent on Concentration Dependence of Hydrodynamic Volumes and GPC Elution Volumes

Effect of Solvent on Concentration Dependence of Hydrodynamic Volumes and GPC Elution Volumes

Beiträge zur gelchromatographischen Fraktionierung im präparativen Maßstab. II. Zum Einfluß der Gelanordnung auf das Elutionsverhalten und die Trennqualität

Effect of solute concentration on hindered diffusion in porous membranes

Contact Info

Product

Resources

About