Association of counterions on polyelectrolytes: Thermodynamic properties in the binding mean spherical approximation

• Published in: Journal of molecular liquids Vol. 270; pp. 14 - 24
• Main Authors: Bernard, O., Simonin, J.-P.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 15-11-2018; Elsevier
• Subjects: Chemical Sciences; or physical chemistry; Theoretical and
• ISSN: 0167-7322; 1873-3166
• DOI: 10.1016/j.molliq.2018.01.122

We present a model for polyelectrolyte solutions within the binding mean spherical approximation. An approach developed previously, to describe polyelectrolytic chain solutions and on the other hand to describe the association of counterions on spherical polyions is generalized, considering both the polyelectrolytic chain formation and the association of counterions on the chains. Thermodynamic properties deduced from this model are presented. The associative part of the Helmholtz energy is deduced from the thermodynamic perturbation theory. Analytic expressions for the electrostatic contributions to the internal and Helmholtz energies are established.
•A model of association of counterions on polyelectrolytes is proposed.•Expressions for charged chains with association are obtained within BiMSA.•Contributions to the internal and Helmholtz energies are established.