Effect of salt valency and concentration on structure and thermodynamic behavior of anionic polyelectrolyte...

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.