Abstract
Conductivity measurements in water and at 25 °C show that the variation of the equivalent conductivity ΛPX with the counter ion concentration CX of some PDDPX polyelectrolytes, poly(1,1-dimethyl-3,5-dimethylene piperidinium, X), for X ≡ Br−, Cl−, \({\text{NO}}_{3}^{ - }\) and F−, is characterized by an inversion in Kohlraush’s law (i.e., \(\forall\)C, ΛPX < ΛPX′ if \(\lambda_{\text{X}}^{ \circ }\) > \(\lambda_{{\text{X}}^{\prime}}^{ \circ }\)), where \(\lambda_{\text{X}}^{ \circ }\) is the conductivity of the counter ion X at infinite dilution. This anomaly cannot be explained in the case of stretched polyions, by the dependence of ΛPX with the degree of dissociation αX, since αX remains quasi-constant at about 0.7 for CX < 2 × 10−2 mol·L−1. On the other hand, such a reversal implies that in the case of a coiled conformation, there is an increase in the ionic condensation, which is incompatible with hydrophobic folding. Similarly, hydrodynamic, electrophoretic and ionic frictions on these PDDPX polyelectrolytes cannot explain this inversion given their weak dependence with the nature of the counter ion X. In fact, for X ≡ Br−, Cl−, \({\text{NO}}_{3}^{ - }\), and for X ≡ F− with CX > 10−3 mol·L−1, this anomaly occurs for PDDPZS+ polyions having a completely stretched chain conformation for which the translational dielectric friction effect on their charged groups becomes important to a variable degree depending on the nature of X. For PDDPF polyelectrolytes, this anomaly is amplified at high dilution because of possible synergy between the ionic dissociation and the hydrophobic character of the polyion, giving rise to a “pearl-necklace conformation” of effective length, L, decreasing with the dilution. In this work, we represent the conformation of polyions by an ellipsoid with a variable eccentricity γp, or by a chain of charged spheres with a variable group radius Rg, or by a pearl necklace model with a variable length L and a variable bead radius. The stability of the general configuration was formally studied according to a new approach based on the principle of superposition of ionic screening effects on the different charged groups.
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References
Onsager, L., Fuoss, R.M.: Irreversible processes in electrolytes. Diffusion, conductance and viscous flow in arbitrary mixtures of strong electrolytes. J. Phys. Chem. 36(11), 2689–2778 (1932)
Kohlrausch, F.: Notiz über die wärmeausdehnung des hartgummi. Progg. Annl. 169, 170 (1873)
Ghazouani, A., Boughammoura, S., M’halla, J.: New interpretation of the dependence of the conductibility of PSS and PAA polyions with the nature of the counterions. Colloid. Polym. Sci. 293, 2995–3011 (2015)
Manning, G.S.: Limiting laws and counterion condensation in polyelectrolyte solutions I. Colligative properties. J. Chem. Phys. 51, 924–933 (1969)
Manning, G.S.: Limiting laws and counterion condensation in polyelectrolyte solutions II. Self-diffusion of the small ions. J. Chem. Phys. 51, 934–935 (1969)
Manning, G.S.: Limiting law for the conductance of the rod model of a salt-free polyelectrolyte solution. J. Phys. Chem. 79(3), 262–265 (1975)
Manning, G.S.: Counterion binding in polyelectrolyte theory. Acc. Chem. Res. 12(12), 443–449 (1979)
M’halla, J.: Polyelectrolytic conductance limiting laws in conformity with the principles of equilibrium and nonequilibrium thermodynamics interdependence between conformation condensation and dielectric friction. J. Mol. Liq. 82, 183–218 (1999)
Vink, H.: Conductivity of polyelectrolyte in very dilute solutions. J. Chem. Soc. Faraday Trans. 77, 2439–2449 (1981)
Muthukumar, M.: 50th Anniversary perspective: a perspective on polyelectrolyte solutions. Macromolecules 50(24), 9528–9560 (2017)
M’halla, J., Besbes, R., Bouazzi, R., Boughammoura, S.: About the singular behavior of the ionic condensation of sodium chondroitin sulfate conductivity study in water and water–dioxane mixture. Chem. Phys. 321, 10–24 (2006)
M’halla, J., Besbes, R., Bouazzi, R., Boughammoura, S.: Ionic condensation of sodium chondroitin sulfate in water–dioxane mixture. J. Mol. Liq. 130, 59–69 (2007)
Manning, G.S.: Limiting laws and counterion condensation in polyelectrolyte solutions 7. Electrophoretic mobility and conductance. J. Phys. Chem. 85, 1506–1515 (1981)
Boughammoura, S., M’halla, J.: Translational dielectric friction on a chain of charged spheres. Sci. World J. 2014, 1–15 (2014)
M’halla, J., Boughammoura, S.: Translation dielectric friction and mobility of ellipsoidal polyions. J. Mol. Liq. 157, 89–101 (2010)
Muthukumar, M.: Dynamics of polyelectrolyte solutions. J. Chem. Phys. 107, 2619–2635 (1997)
Dobrynin, A.V., Rubinstein, M.: Theory of polyelectrolytes in solutions and at surfaces. Prog. Polym. Sci. 30, 1049–1118 (2005)
Boughammoura, S., M’halla, J.: Generalization of the model of Debye–Hückel according to a matrix approach. Application to the calculation of the potential of mean force in the case of electrolytes, polyelectrolytes and colloids. J. Mol. Liq. 214, 196–206 (2016)
Stillinger Jr., F.H., Lovett, R.: Ion-pair theory of concentrated electrolytes. J. Chem. Phys. 48, 3858–3868 (1968)
Katchalsky, A., Alexandrowicz, Z., Kedem, O.: In: Conway, B.E., Barradas, R.G. (eds.) Chemical Physics of Ionic Solutions. Wiley, New York (1966)
Blum, L.: Mean spherical model for asymmetric electrolytes. Mol. Phys. 30, 1529–1535 (1975)
Blum, L., Hoye, J.S.: Mean spherical model for asymmetric electrolytes. 2. Thermodynamic properties and the pair correlation function. J. Phys. Chem. 81, 1311–1313 (1977)
Robinson, R.A., Stokes, R.H.: Electrolyte Solutions. Butterworths Scientific Publications, London (1959)
Fuoss, R., Accascina, F.: Electrolytic conductance. Interscience Publishers, New York (1969)
Ben Mahmoud, S., Essafi, W., Abidelli, A., Rawiso, M., Boue, F.: Quenched polyelectrolytes with hydrophobicity independent from chemical charge fraction: a SANS and SAXS study. Arab. J. Chem. 10, 1001–1014 (2017)
Colby, R.H.: Structure and linear viscoelasticity of flexible polymer solutions: comparison of polyelectrolyte and neutral polymer solutions. Rheol. Acta 49, 425–442 (2010)
Boughammoura, S., M’halla, J.: Estimation of the hydrophobic reactivity of SDS micelles by the use of BPh −4 anions. J. Mol. Liq. 175, 148–161 (2012)
Qian, H., Elson, E.L.: Quantitative study of polymer conformation and dynamics by single-particle tracking. Biophys. J. 76, 1598–1605 (1999)
Hubbard, J.B., Douglas, F.: Hydrodynamic friction of arbitrarily shaped Brownian particles. Phys. Rev. E 47, 2983–2986 (1993)
Fuoss, R.M.: Dependence of the Walden product on dielectric constant. Proc. Natl. Acad. Sci. USA 45, 807 (1959)
Boyd, R.H.: Extension of Stokes’ Law for ionic motion to include the effect of dielectric relaxation. J. Chem. Phys. 35, 1281–1283 (1961)
Zwanzig, R.: Dielectric friction on a moving ion. J. Chem. Phys. 38, 1603–1605 (1963)
Hubbard, J.B., Onsager, L.: Dielectric dispersion and dielectric friction in electrolyte solutions I. J. Chem. Phys. 67, 4850–4857 (1977)
Hubbard, J.B.: Dielectric dispersion and dielectric friction in electrolyte solutions. II. J. Chem. Phys. 68, 1649–1664 (1978)
Nostro, L., Ninham, B.W.: Hofmeister phenomena: an update on ion specificity in biology. Chem. Rev. 112, 2286–2322 (2012)
Conway, B.E.: Ionic Hydration in Chemistry and Biophysics. Studies in Physical and Theoretical Chemistry, vol. 12. Elsevier Scientific Publishing Company, Amsterdam and New York (1981)
Rios, H.E., Sepulveda, L.N., Gamboa, C.I.: Electrical conductivity of cationic polyelectrolytes in aqueous solution. J. Polym. Sci. Pol. Phys. B. 28, 505–511 (1990)
Lahoiya, N.: Modélisation de la condensation ionique selon le modèle de la chaîne linéaire de sphères chargées. Master memory. Faculty of Sciences. University of Monastir, Tunisia (2015)
Nagaya, J., Minakata, A., Tanioka, A.: Conductance and counterion activity of ionene solutions. Langmuir 15(12), 4129–4134 (1999)
Luksic, M., Hribar-Lee, B., Vlachy, V.: Interplay of ion-specific and charge-density effects in aqueous solutions of weakly charged ionenes as revealed by electric-transport measurements. J. Phys. Chem. B 114(32), 10401–10408 (2010)
Zelikin, A.N., Davydova, O.V., Akritskaya, N.I., Kargov, S.I., Izumrudov, V.A.: Conformation of polyelectrolyte chains in dilute aqueous solutions investigated by conductometry. Influence of molecular mass and charge density of the chains on conformation of symmetrical aliphatic ionene bromides. J. Phys. Chem. B 108(1), 490–495 (2004)
Druchok, M., Malikova, N., Rollet, A.-L., Vlachy, V.: Counter-ion binding and mobility in the presence of hydrophobic polyions: combining molecular dynamics simulations and NMR. AIP Adv. 6, 065214 (2016)
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The authors are grateful to the General Direction of Scientific Research of Tunisia (D.G.R.S.T) for assistance and supporting grants.
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M’halla, J., Boughammoura, S. & Ghazouani, A. Some New Contributions to the Theory of Polyelectrolyte Solutions: Prediction of Polyion Conformation and Interpretation of Some Deviations from Kohlrausch’s Law According to the Superposition Principle and the Dielectric Friction Effect. J Solution Chem 48, 1685–1715 (2019). https://doi.org/10.1007/s10953-019-00916-9
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DOI: https://doi.org/10.1007/s10953-019-00916-9