The effect of counter‐ion substitution on the transport properties of polyelectrolyte solutions

Magdelénat, H.; Turr, P.; Tivant, P.; Chemla, M.; Menez, Raphael; Drifford, M.

doi:10.1002/bip.1979.360180114

Cited by 42 publications

(28 citation statements)

References 10 publications

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“…Using eq 5, we solve for C H +, using 3.27 × 10 -7 cm 2 s -1 for D HCS 29, 30 6.22 × 10 -5 cm 2 s -1 for D a , and the above value of D H +. Using this value of C H +, the pK a is calculated to be 3.53, which is close to the value of 3.7 from colorimetric measurements in the same range of polyelectrolyte and supporting electrolyte concentrations ( Figure 3).…”

Section: Resultsmentioning

confidence: 99%

Voltammetric Studies of Counterion Transport in Solutions of Chondroitin Sulfate

and

Osteryoung

1996

J. Phys. Chem.

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The transport of hydrogen counterions was studied in solutions of a linear polyelectrolyte, chondroitin sulfate, CS, by voltammetric measurements at a platinum disk microelectrode. The use of microelectrodes enables voltammetry of the counterion in solutions with little or no supporting electrolyte over a wide range of polyelectrolyte concentrations. The voltammetric interactions of counterions with polyions diminish transportlimited current for reduction of electroactive counterions, as shown by comparing results for a polymeric strong acid, poly(styrenesulfonic acid), and simple strong acids. The experimental results agree reasonably well with Manning's theory, which describes the effect of ionic interactions on the transport of simple ions in the presence of polyelectrolytes. The data agree equally well with a much simpler semiempirical theory. The experimentally determined limiting value (no supporting electrolyte) of the transport ratio, D/D o , is 0.53, where D and D o are the diffusion coefficients of free hydrogen ion with and without CS. The pK a of the carboxyl group of CS is estimated to vary from 3.5 to 5.7 in the range 0.1-0.001 M of ionic strength.

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Section: Resultsmentioning

confidence: 99%

Voltammetric Studies of Counterion Transport in Solutions of Chondroitin Sulfate

and

Osteryoung

1996

J. Phys. Chem.

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“…The nonuniform distribution of the fixed charge leads to the nonuniform distribution of the electric potential that hinders the ion motion. The influence of the fixed charge heterogeneity on the diffusion coefficient has been studied experimentally and theoretically for ionites [51,52] and biopolymers [53].…”

Section: Influence Of the Fixed Charge Distribution On The Ion Mobilitymentioning

confidence: 99%

Charge density distribution at interfaces between polyelectrolyte layers and aqueous solutions—Experimental access and limitations of traditional electrokinetics

Dukhin

Zimmermann

Werner

2008

Journal of Colloid and Interface Science

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“…Studies of the self-diffusion of small, solvent or solute, molecules have been extensively used to investigate colloidal systems containing polymers [1][2][3][4], polyelectrolytes [5][6][7], proteins [8][9][10], micelles, normal [11,12] or reversed [13]. The method has also been applied to microemulsions [14,15], liquid crystals [16,17] and gels [18], and the self-diffusion is obviously of importance also for the study of porous media [19].…”

Section: Introductionmentioning

confidence: 99%

Self-diffusion of small molecules in colloidal systems

Jönsson¹,

Wennerström²,

Nilsson³

et al. 1986

Colloid & Polymer Sci

280

241

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Abstract:The self-diffusion of small molecules in colloidal systems is calculated using the cell model to describe the effect of varying concentration of colloidal particles. The relevant boundary conditions are found using arguments from the thermodynamics of irreversible processes. From a general description of the self-diffusion in systems with spherically symmetrical particles we derive expressions for the concentration dependence of the effective self-diffusion coefficient De~t for several cases of practical importance. It is shown that when the molecule studied is strongly attracted to the particle a minimum in D ~ff is expected around volume fraction 4~ = 0.35. It is also shown that the often made distinction between free and bound molecules is often problematic and a more general description is proposed. The obstruction effect generated by the excluded volume is discussed both for spherical and spheroidal systems. It is pointed out that the often used formula due to Wang ((1954) J Amer Chem Soc 76:4755) is incorrect for self-diffusion and for the obstruction factor for spheres we obtain (1 + 0.5 ~)-1. This expresion is tested both by experiments on water diffusion in systems containing latex particles and through computer simulations and it is found valid over a wide concentration range. For prolate ellipsoids the obstruction factor is not greatly different from that for spheres, while for oblate aggregates the limking obstruction factor of 2/3 can be obtained at low concentrations. It is demonstrated that this effect can be used to distinguish between different aggregate shapes. It is also shown that the disorder present in a solution of colloidal particles leads to a decrease in the obstruction effect.

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The effect of counter‐ion substitution on the transport properties of polyelectrolyte solutions

Cited by 42 publications

References 10 publications

Voltammetric Studies of Counterion Transport in Solutions of Chondroitin Sulfate

Voltammetric Studies of Counterion Transport in Solutions of Chondroitin Sulfate

Charge density distribution at interfaces between polyelectrolyte layers and aqueous solutions—Experimental access and limitations of traditional electrokinetics

Self-diffusion of small molecules in colloidal systems

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