The Second Virial Coefficient of Polyelectrolytes

Takahashi, Akira; Kato, Tadaya; Nagasawa, Mitsuru

doi:10.1021/j100866a600

Cited by 201 publications

(148 citation statements)

References 7 publications

(8 reference statements)

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“…The average molecular weight (M) of the sample was 70000. The molecular weight reported by the manufacturer agreed well with that determined in the present study obtained in presence of 0.05 M sodium chloride (NaCl) at 298.15 K using the Mark-Houwink relationship, [13] h ½ ¼ 1:39x10 À4 M 0:72 , where M is the average molecular weight. The absorption coefficient of the NaPSS solutions used at 261 nm, which is considered to be a characteristic indicator of the sample purity, [14] is found to be 400 dm 3 cm À1 mol À1 .…”

Section: Experimental Part Materialssupporting

confidence: 89%

Solvodynamic Properties of Sodium Polystyrenesulfo‐nate in Methanol‐Water Mixed Solvent Media in Absence and in the Presence of a Salt Using Viscometric Method

Bhattarai¹,

Das²

2012

Macromolecular Symposia

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Summary: Linear extrapolation of the reduced viscosity values of uncharged polymer solutions as the concentration approaches zero constitutes the basis for the traditional method for the determination of the intrinsic viscosities of polymer solutions. While this method works well for uncharged polymer solutions, it fails completely for polyelectrolyte solutions especially in absence and also in presence of small amount of an added electrolyte. A very convenient method has recently been proposed by Wolf (Wolf, Macromol. Rapid Commun. 2007, 28, 164) to determine the intrinsic viscosities of polyelectrolyte solutions on the basis of the laws of phenomenological thermodynamics applied to the viscosity of polymer solutions. In spite of the success and the convenience of this method, this has so far been applied to a limited number of polyelectrolyte systems by the Wolf group alone (Wolf, In order to improve the situation, we have measured the viscosities of an anionic polyelectrolyte, sodium polystyrenesulfonate, in methanol-water mixed solvent media both in absence and in the presence of an electrolyte, sodium chloride. The results show that the experimental data fit well with the Wolf model and thus allow the calculation of intrinsic viscosities, which provide important insight about the dependence of the polyion conformation on solvent composition as well as on the concentration of the added electrolyte. This new evaluation method, thus, proves to be very useful to a better understanding of the rheological behaviour of the polyelectrolyte system investigated.

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Section: Experimental Part Materialssupporting

confidence: 89%

Solvodynamic Properties of Sodium Polystyrenesulfo‐nate in Methanol‐Water Mixed Solvent Media in Absence and in the Presence of a Salt Using Viscometric Method

Bhattarai¹,

Das²

2012

Macromolecular Symposia

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“…We have used qb = 0.86 x 10 z3 mole -i , the mean value for the system polyacrylateNaC1-H20 (34), also for our system. This value is in good agreement with data of Takahashi et al (35) for sodium polystyrene sulfonate with NaC1 in water in the corresponding expansion interval. We carried out the necessary viscosity measurements and in order to obtain straight lines in the extrapolation to [~] we used the isoionic dilution technique of Pals and Hermans (36).…”

supporting

confidence: 92%

Electric transport properties of alkali polymethacrylates in alkali bromide solutions

Drift

Overbeek

1979

Journal of Colloid and Interface Science

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Electric mobilities of polyions, bromide ions, and alkali ions have been determined in solutions of Li, Na, and K salts of polymethacrylic acid (PMA) in aqueous solutions of the corresponding bromide of concentrations varying from 0.001 to 0.1 M. The Hittorf method was used for the determination of the mobilities of the PMA ion and of the Br-ion. The mobilities of the alkali ions followed from these two mobilities and the conductivity. A few moving boundary experiments have been carried out with tetramethylammonium PMA. The mobility of PMA was independent of the PMA concentration and of the kinds of cations and changed only slowly with the degree of neutralization. The bromide mobility decreased slowly with increasing PMA concentration. The interpretation was based upon a separation of the contributions from the polyelectrolyte salt and those of the supporting electrolytes. The mobilities of the counterions that neutralized the polyions were very low and in several cases even negative. Electrophoretic retardations varied from about 20 to 70 12 -~ cmz eq -~. By using the relaxation correction as found from conductivity data we could interpret the mobility of the PMA ion as that of a cylinder of 0.35-nm radius surrounded by a solvation layer of 0.2-to 0.3-nm thickness. For bromide concentrations up to 0.03 M the agreement was excellent; at a 0.1 M bromide concentration binding of about 25% of the counterions to the polyions had to be assumed to reconcile the model calculations with the experiments. Intrinsic viscosities of NaPMA in NaBr solutions have been used to obtain an estimate of the overall size of the polyelectrolyte coil and to justify the cylinder model.

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“…Most of the nonideal behavior of linear polyelectrolytes is compensated by the strong electrostatic interaction between charges, but the contribution of the polymeric character cannot be neglected. [116] There is a considerable amount of theoretical work on chain expansion and virial coefficients of charged homo and copolymers. A brief review of theories of polyelectrolyte conformation has recently been presented by Stigter and Dill.…”

Section: Coil-globule Transition Of Polyelectrolytesmentioning

confidence: 99%

Coil‐Globule Collapse in Flexible Macromolecules

Baysal

Karasz

2003

Macro Theory & Simulations

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The transition of a solvated flexible macromolecular chain from random coil behavior in the θ‐state to a globular compact form in the collapsed state has been the subject of extensive theoretical and experimental studies. Most of the coil‐globule transition studies of macromolecules have concentrated on the prototypical polystyrene‐cyclohexane system. However, chain contractions reported in this system have been around 75% of those in the unperturbed θ‐state. This relatively small decrease in size does not satisfy the criterion for a densely packed, collapsed globule. Experimentally, the collapse from a coil to a true compact globular state has now been established for two flexible macromolecules: poly(N‐isopropylacrylamide) in water and poly(methyl methacrylate) in various solvents. In this contribution, we review recent theoretical studies covering phenomenological and Langevin models as well as computer simulations. In addition, we outline recent experimental studies of the coil‐globule transition of various flexible polymers, copolymers, and polyelectrolytes.Expansion factor, α, versus temperature for NaPSS in 4.17 M aqueous NaCl solution. (•): NaPSS‐1, (○): NaPSS‐2.imageExpansion factor, α, versus temperature for NaPSS in 4.17 M aqueous NaCl solution. (•): NaPSS‐1, (○): NaPSS‐2.

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The Second Virial Coefficient of Polyelectrolytes

Cited by 201 publications

References 7 publications

Solvodynamic Properties of Sodium Polystyrenesulfo‐nate in Methanol‐Water Mixed Solvent Media in Absence and in the Presence of a Salt Using Viscometric Method

Solvodynamic Properties of Sodium Polystyrenesulfo‐nate in Methanol‐Water Mixed Solvent Media in Absence and in the Presence of a Salt Using Viscometric Method

Electric transport properties of alkali polymethacrylates in alkali bromide solutions

Coil‐Globule Collapse in Flexible Macromolecules

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