Effects of distribution of charge over the polyelectrolyte chain on the structure and osmotic pressure of salt-free solutions

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria Pub Date : 2025-02-18 DOI:10.1016/j.fluid.2025.114391

Kristina Nikiforova, Alexey Victorov

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Abstract

The impact of structural details of polyelectrolyte molecules on the behavior of solutions and melts has been subject of growing interest motivated by a key role of such systems in many fields of science and by the need to tailor polyelectrolyte materials for various specific applications. In this work, we applied the model based on the recently developed statistical-field theory in the Random Phase Approximation (RPA) to examine the impact of structural details of a macromolecule on the structure and osmotic pressure of a salt-free aqueous solution. We consider different distributions of charged and neutral monomeric units along the backbone of polyelectrolyte chain, different hard-sphere diameters of these units and counterions, as well as the effects of chain elasticity and asymmetric distribution of electrical charge inside the ions. Taking realistic molecular characteristics of a macromolecule, we examine how the calculated partial structure factors and the osmotic pressure of a salt-free solution respond to variations of the polyelectrolyte structural details over a wide concentration range, from dilute to concentrated solutions. Calculated results are compared with computer simulation and experimental data.

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来源期刊

Fluid Phase Equilibria 工程技术-工程：化工

CiteScore

5.30

自引率

15.40%

发文量

223

审稿时长

53 days

期刊介绍： Fluid Phase Equilibria publishes high-quality papers dealing with experimental, theoretical, and applied research related to equilibrium and transport properties of fluids, solids, and interfaces. Subjects of interest include physical/phase and chemical equilibria; equilibrium and nonequilibrium thermophysical properties; fundamental thermodynamic relations; and stability. The systems central to the journal include pure substances and mixtures of organic and inorganic materials, including polymers, biochemicals, and surfactants with sufficient characterization of composition and purity for the results to be reproduced. Alloys are of interest only when thermodynamic studies are included, purely material studies will not be considered. In all cases, authors are expected to provide physical or chemical interpretations of the results. Experimental research can include measurements under all conditions of temperature, pressure, and composition, including critical and supercritical. Measurements are to be associated with systems and conditions of fundamental or applied interest, and may not be only a collection of routine data, such as physical property or solubility measurements at limited pressures and temperatures close to ambient, or surfactant studies focussed strictly on micellisation or micelle structure. Papers reporting common data must be accompanied by new physical insights and/or contemporary or new theory or techniques.