Ion-specific and charge effects in counterion binding to poly(styrenesulfonate) anions
Laboratory of Physical Chemistry, Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000 Zagreb, Croatia.Physical Chemistry Chemical Physics (Impact Factor: 4.49). 09/2011; 13(34):15610-8. DOI: 10.1039/c1cp21291e
In order to obtain a deeper insight into effects occurring when an electrolyte solution is added to a solution of a strong polyelectrolyte, the microcalorimetric and potentiometric titrations of poly(sodium 4-styrenesulfonate) (Na(+)PSS(-)) solution with different alkali, earth-alkali and tetraalkylammonium nitrate, perchlorate and chloride solutions were performed. From the calorimetric titrations the differences in sign and magnitude of enthalpy change upon addition of various electrolytes were observed depending on the salt used. Potentiometric titrations using a sodium ion selective electrode have revealed that addition of an electrolyte is accompanied by the increase in sodium activity until a certain critical value is reached, which seems to be the consequence of counterion substitution on the polyelectrolyte chain. In the case of addition of lithium and sodium salts the experimental results for ΔH of mixing can be qualitatively correctly explained by the Poisson-Boltzmann and Monte Carlo calculations based on the continuum solvent models. This is not the case for the mixtures with KNO(3), RbNO(3) and CsNO(3) salts. The results suggest that the ion-specific effects, associated with the changes in the water structure, have to be taken into account when thermodynamic properties of polyelectrolytes in solution are concerned. The calorimetric results imply that the enthalpically observed cation specificity for binding to a poly(styrenesulfonate) group could be correlated with corresponding cation hydration enthalpies. The counterion substitution of sodium with divalent cations was found to be endothermic, which is in qualitative agreement with the electrostatic theory.
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ABSTRACT: Aliphatic x,y-ionenes are polyelectrolytes in which x and y denote the numbers of methylene groups separating quaternary ammonium ions. They represent useful model substances for studying hydrophobic and charge effects in aqueous solutions. We used isothermal titration calorimetry to measure the enthalpies of mixing, ΔH(mix), of 3,3- and 6,6-ionene fluorides and bromides with low molecular weight salts (NaF, NaCl, NaBr, and NaI) at 298 K in water. The signs and magnitudes of the measured enthalpies depend on the hydrophobicity of the ionene and on the nature of the added salt. For example, addition of sodium fluoride to solutions of 3,3- and 6,6-ionene fluorides produced endothermic effects, while addition of sodium bromide to 3,3-ionene bromide resulted in a strong exothermic effect. Interestingly, mixing of 6,6-ionene bromide and NaBr solutions in water gave a small exothermic heat effect. Polyelectrolyte theories, based on continuum-solvent models, predict enthalpies of mixing to be positive (endothermic) for all the solutions examined in this work. The ion-specific effect is more strongly expressed in ionene solutions with higher charge density (3,3-ionene). The most important result of this work is the finding that the enthalpy of mixing of 3,3- (and of 6,6-ionene) fluorides with sodium halides can be expressed as a linear function of the enthalpy of hydration of the halide counterions. The experimental results were complemented with an explicit water molecular dynamics simulation of solutions of oligoions modelling 3,3- and 6,6-ionenes. The computer simulation results for various nitrogen-counterion pair distribution functions were in most cases consistent with the enthalpy measurements.
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ABSTRACT: Enthalpies of mixing of aliphatic 3,3 and 6,6-ionene fluorides with low molecular weight salts (sodium formate, acetate, nitrate, chlorate(v), and thiocyanate), all dissolved in water, were determined. In addition, to complement our previous study (Lukšič et al., Phys. Chem. Chem. Phys., 2012, 14, 2024), new measurements were performed where aqueous solutions of 3,3 and 6,6-ionene bromides were mixed with solutions of sodium fluoride, chloride, bromide, and iodide. Electrostatic theory, based on Manning's limiting law or the Poisson-Boltzmann equation, predicted the enthalpy of mixing to be endothermic in all the cases, while experiments showed that this is not always true. When an aqueous solution of 3,3-ionene fluoride was mixed with a solution of sodium fluoride (or formate and acetate) in water, the effect was indeed endothermic. For all other salts, i.e. sodium chlorate, nitrate, and thiocyanate, heat was released upon mixing. The situation was similar for 6,6-ionene fluoride solutions with an exception of mixing with sodium chlorate, where the effect was endothermic. The enthalpy of mixing was strongly correlated with the enthalpy of hydration of the counterion of the low molecular weight salt. A lyotropic series, similar to that of Hofmeister, was obtained. To examine also the effect of co-ions, ionene bromides were titrated with tetramethyl-, tetraethyl-, or tetrapropylammonium bromides. The enthalpy was exothermic for all mixtures while, somewhat unexpectedly, the co-ion specific effect was quite strong.
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ABSTRACT: Enthalpies of dilution of aqueous solutions of aliphatic 6,12-- and 12,12--ionene bromides and fluorides, and enthalpies of mixing with low molecular--weight salts, such as sodium fluoride and bromide, are determined. In the second part of the study, the various x,y--ionenes (x,y are numbers of methylene groups between the adjacent charges) with fluoride, bromide, and iodide counterions are mixed with aqueous sodium sulfate solution. The polyelectrolytes examined in this part of the work are 3,3--, 6,9--, 6,12--, and 12,12--ionenes. Comparison with theoretical results, based on the Poisson--Boltzmann cell model, is presented. The theory predicts for the enthalpy of dilution to be exothermic and enthalpy of mixing endothermic, while experiments show that signs of the heat effects depend on the nature of counterion of the added salt, as also on the hydrophobicity (numbers x,y of methylene groups) of the ionene. We show that the salts when ordered by heat effects produced by mixing of NaF and NaBr with 3,3--, 6,9--, or 6,12--ionene fluorides and bromides, follow the opposite ordering, than in the case when the same alkali halide salts are mixed with more hydrophobic 12,12--ionene salts. The results for enthalpy of mixing of ionenes under study with Na2SO4 follow the same order as obtained for monovalent salts.
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