Polyelectrolyte solutions are modeled as freely tangent-jointed, charged hard-sphere chains and corresponding counterions in a continuum medium with permitivity ε. By adopting the sticky-point model, the Helmholtz function for polyelectrolyte solutions is derived through the -particle cavity-correlation function (CCF) for chains of sticky, charged hard spheres. The -CCF is approximated by a product of effective nearest-neighbor two-particle CCFs; these are determined from the hypernetted-chain and mean-spherical closures (HNC/MSA) inside and outside the hard core, respectively, for the integral equation theory for electrolytes. The colligative properties are given as explicit functions of a scaling parameter Γ that can be estimated by a simple iteration procedure. Osmotic pressures, osmotic coefficients, and activity coefficients are calculated for model solutions with various chain lengths. They are in good agreement with molecular simulation and experimental results.
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8 January 1998
Research Article|
January 08 1998
A molecular-thermodynamic model for polyelectrolyte solutions
Jianwen Jiang;
Jianwen Jiang
Thermodynamics Research Laboratory, East China University of Science and Technology, Shanghai 200237, China
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Honglai Liu;
Honglai Liu
Thermodynamics Research Laboratory, East China University of Science and Technology, Shanghai 200237, China
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Ying Hu;
Ying Hu
Thermodynamics Research Laboratory, East China University of Science and Technology, Shanghai 200237, China
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J. M. Prausnitz
J. M. Prausnitz
Department of Chemical Engineering, University of California, Berkeley, and Chemical Sciences Division, Lawrence Berkeley Laboratory, University of California, Berkeley, California 94720
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J. Chem. Phys. 108, 780–784 (1998)
Article history
Received:
June 27 1997
Accepted:
October 02 1997
Citation
Jianwen Jiang, Honglai Liu, Ying Hu, J. M. Prausnitz; A molecular-thermodynamic model for polyelectrolyte solutions. J. Chem. Phys. 8 January 1998; 108 (2): 780–784. https://doi.org/10.1063/1.475438
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