STUDIES OF POLYELECTROLYTE SOLUTIONS .3. CORRELATIONS BETWEEN THE 2ND AND THE 3RD VIRIAL-COEFFICIENT

DC FieldValueLanguage
dc.contributor.authorNORDMEIER, E
dc.date.accessioned2021-12-23T16:04:34Z-
dc.date.available2021-12-23T16:04:34Z-
dc.date.issued1993
dc.identifier.issn00323896
dc.identifier.urihttps://osnascholar.ub.uni-osnabrueck.de/handle/unios/6491-
dc.description.abstractCombined Donnan equilibria and static light scattering experiments have been performed on aqueous solutions of poly(styrene sulfonate), PSS, in the presence of low molar mass electrolytes. Two systems were investigated, namely PSS/Na and PSS/Pb/H. The coion was nitrate. Additionally, the molar mass, M(w), of PSS was varied in the range of 3.20 x 10(5) to 1.22 x 10(6) Da. Donnan equilibria experiments yield the degrees of binding, THETA1 and THETA2, for the uni- and the divalent counterions, THETA1 and THETA2 increase with increasing ionic strength, but they are independent on M(w) within the experimental error. Static light scattering yields the molar mass, M(w) the radius of gyration, [S2]z1/2, and the second and third virial coefficients, A2 and A3. Data analysis is made in two ways: (1) by using the brute-, and (2) by using the net polyion concentrations. Here, the term `'brute'' stands for the naked polyion skeleton, while the net polyion concentration is the concentration which includes the counterions bound to the polyelectrolytes. C(brute) is known from the sample preparation. C(net) can be calculated from THETA1 and THETA2. It is found: (1) M(w,net) is significantly larger than M(w,brute); (2) [S2]z,net1/2 and [S2]z,brute1/2 are identical within the experimental error, and (3) A2,net and A3,net are significantly smaller than A2,brute and A3,brute. The molar mass dependencies of [S2]z,net1/2, A2,net, and A3,net can be well described by power laws [S2]z,net1/2 = K[S]z . M(w,net)v[S]z, A2,net = K(A2) . M(w,net)v(A2) and A3,net = K(A3) . M(w,net)v(A3). The exponents, v[S]z and v(A3), decrease with increasing ionic strength while v(A2) increases. Interestingly, v(A3) is significantly larger than 2v(A2) 1. This suggests that A3 is not proportional to A2(2) . M(w) as predicted by some theories. The nature of the mentioned effects could be established, however, only in part. An interpretation by the conventionally excluded volume theory was not successful. Indeed, a universal functon, PSI, incorporating effects such as molar mass, degree of dissociation, and solvent quality, is found; but none of the present theories is suitable to describe the experimental data satisfactory. In conclusion, a completely new theoretical concept will be necessary for the future.
dc.language.isoen
dc.publisherSOC POLYMER SCIENCE JAPAN
dc.relation.ispartofPOLYMER JOURNAL
dc.subject2ND AND 3RD VIRIAL COEFFICIENT
dc.subjectBRUTE AND NET QUANTITIES
dc.subjectCOUNTERION CONDENSATION
dc.subjectDEPENDENCE
dc.subjectDNA
dc.subjectEXCLUDED VOLUME
dc.subjectLIMITING LAWS
dc.subjectMIXTURES
dc.subjectPOLY(STYRENE SULFONATE)
dc.subjectPOLY-ELECTROLYTE SOLUTIONS
dc.subjectPolymer Science
dc.subjectSCATTERING
dc.subjectSTATIC LIGHT SCATTERING
dc.titleSTUDIES OF POLYELECTROLYTE SOLUTIONS .3. CORRELATIONS BETWEEN THE 2ND AND THE 3RD VIRIAL-COEFFICIENT
dc.typejournal article
dc.identifier.doi10.1295/polymj.25.1
dc.identifier.isiISI:A1993KH77000001
dc.description.volume25
dc.description.issue1
dc.description.startpage1
dc.description.endpage17
dc.publisher.placeTSUKIJI DAISAN NAGAOKA BLDG, 2-4-2 TSUKIJI, CHUO-KU, TOKYO 104, JAPAN
dcterms.isPartOf.abbreviationPolym. J.
dcterms.oaStatusBronze
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