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Effect of salt valency and concentration on structure and thermodynamic behavior of anionic polyelectrolyte Na+-polyethacrylate aqueous solution

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Abstract

The intermolecular structure and solvation enthalpy of anionic polyelectrolyte atactic Na+-polyethacrylate (PEA) in aqueous solution, as a function of added salt concentration C s (dilute to concentrated) and valency (NaCl versus CaCl2), were investigated via molecular dynamics simulations with explicit-ion-solvent and atomistic polymer description. An increase in C s leads to a decrease in α, which stabilizes to a constant value beyond critical C s. A significant reduction in R g in the presence of CaCl2 salt was observed, due to ion bridging of PEA by Ca2+ ions, in agreement with results available in literature on other similar polycarboxylates. An increase in salt valency reduces the value of critical C s for the onset of stabilization of the overall size and shape of the polymer chain. The critical C s ratio for the divalent to monovalent salt case is in excellent agreement with results of Langevin dynamics studies on model systems available in the literature. PEA–water H-bond half-life increases with C s for CaCl2, but no appreciable effect is seen for NaCl. The hydration of PEA becomes stronger in the presence of divalent salt. The strength of H-bond interaction energy is greater for cations as compared to anions of the salt. The salt cation effect in displacing water molecules from the vicinity of PEA, with increase in C s, is greater for NaCl solution. The decrease in water coordination to PEA carboxylate groups, due to increased C s, is more pronounced in NaCl solution. The nature of the behavior of the solvation enthalpy of PEA and the type of intermolecular interactions contributing to it, is in agreement with experimental observations from the literature. The hydration enthalpy of PEA in divalent CaCl2 aqueous salt solution is more exothermic compared to monovalent NaCl salt solution, in agreement with experimental data. The solvation of PEA is thermodynamically more favorable in the case of CaCl2 solution. The exothermic solvation enthalpy, H-bond lifetime, number of H-bonds and H-bond interaction energy are greater in magnitude in CaCl2 aqueous solution.

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Acknowledgments

The authors appreciate the availability of the Virgo supercomputing cluster at the Indian Institute of Technology Madras, on which most of the simulations were carried out. The structural and dynamic analysis as well some of the preparatory NVT and NPT simulations were carried out on individual Linux workstations.

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  1. Macromolecular Modeling and Simulation Laboratory, Department of Chemical Engineering, Indian Institute of Technology (IIT) Madras, Chennai, 600036, India

    Praveenkumar Sappidi & Upendra Natarajan

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  1. Praveenkumar Sappidi
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  2. Upendra Natarajan
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Correspondence to Upendra Natarajan.

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Sappidi, P., Natarajan, U. Effect of salt valency and concentration on structure and thermodynamic behavior of anionic polyelectrolyte Na+-polyethacrylate aqueous solution. J Mol Model 22, 274 (2016). https://doi.org/10.1007/s00894-016-3144-4

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