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• W2011051917 abstract "Combined 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, Mw, of PSS was varied in the range of 3.20×105 to 1.22×106 Da. Donnan equilibria experiments yield the degrees of binding, Θ1 and Θ2, for the uni- and the divalent counterions. Θ1 and Θ2 increase with increasing ionic strength, but they are independent on Mw within the experimental error. Static light scattering yields the molar mass, Mw, 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. Cbrute is known from the sample preparation. Cnet can be calculated from Θ1 and Θ2. It is found: (1) Mw,net is significantly larger than Mw,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 , , and . The exponents, v〈S〉z and vA3, decrease with increasing ionic strength while |vA2| increases. Interestingly, vA3 is significantly larger than 2vA2+1. This suggests that A3 is not proportional to A22·Mw 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, Ψ, 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." @default.
• W2011051917 created "2016-06-24" @default.
• W2011051917 creator A5068647765 @default.
• W2011051917 date "1993-01-01" @default.
• W2011051917 modified "2023-10-17" @default.
• W2011051917 title "Studies of Polyelectrolyte Solutions III. Correlations between the Second and the Third Virial Coefficient" @default.
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• W2011051917 doi "https://doi.org/10.1295/polymj.25.1" @default.
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