Free enthalpies, enthalpies, and entropies of dilution of aqueous solutions of alkaline earth poly(styrenesulfonates) at different temperatures

Vesnaver, Gorazd; Kranjc, Zdenka; Pohar, C.; Škerjanc, Jože

doi:10.1021/j100298a024

Cited by 16 publications

(16 citation statements)

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“…30͒, it is worthwhile to discuss the theoretical results in light of the existing experimental data. Heats of dilution of alkaline polystyrenesulfonates as measured by Skerjanc and co-workers [37][38][39] are almost in quantitative agreement with the PB cell model results in the case of strongly hydrated ions as Li + or H + . On the other hand, for weakly hydrated ions as Cs + the measurements depart from the theory.…”

Section: A Thermodynamic Propertiessupporting

confidence: 81%

Counterion-counterion correlation in the double layer around cylindrical polyions: Counterion size and valency effects

Piñero

Bhuiyan

Reščič

et al. 2007

The Journal of Chemical Physics

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Monte Carlo simulation and Poisson-Boltzmann results on some aspects of structure and thermodynamics of aqueous polyelectrolyte solutions are presented. The polyelectrolyte solution is described by an infinitely long cylindrical polyion surrounded by counterions modeled as rigid ions moving in a continuum dielectric. Ion-ion correlations in the form of volume average of the counterion-counterion distribution function in the double layer surrounding the polyion are reported for mono- and divalent counterions and for a range of polyion concentrations and charge density parameters in each case. These results confirm again strong influence of the charge density parameter of polyions on properties of polyelectrolyte solutions. The structural information is supplemented by the calculated thermodynamic properties such as osmotic coefficients and heats of dilutions; the latter quantity has not been examined yet in detail by computer simulations. The results are discussed in view of the existing experimental data from the literature for these properties.

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Section: A Thermodynamic Propertiessupporting

confidence: 81%

Counterion-counterion correlation in the double layer around cylindrical polyions: Counterion size and valency effects

Piñero

Bhuiyan

Reščič

et al. 2007

The Journal of Chemical Physics

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“…[4,9,58,59]. The two theories are in good agreement with measured data for strongly hydrated monovalent ions such as H + and Li + but not for others.…”

Section: Continuum-solvent Theoriessupporting

confidence: 69%

“…The calculated ∆H D values are always negative, while experimentally determined values of this quantity can be either positive or negative, depending on the polyelectrolyte-counterion pair and the temperature of observation [9,12,13,60]. Poor agreement between the Poisson-Boltzmann theory and experiment for ∆H D is obtained for solutions containing divalent counterions [59]. It has been demonstrated recently that using a more exact statistical mechanical treatment (e.g., MC simulation) of the model considering polyions as hard cylinders, the [25]; ( ) ionenes [35]; ( ○ ) polyphosphates [2]; ( ) carboxymethyl cellulose [2]; ( ) polyacrylates [27,28]; ( ) polystyrenesulfonic acid, where the charge on the polyions was partly blocked by addition of a surfactant [29].…”

Section: Continuum-solvent Theoriesmentioning

confidence: 88%

Polyelectrolyte hydration: Theory and experiment

Vlachy

2008

Pure and Applied Chemistry

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A short review of recent theoretical and experimental advances in studies of polyelectrolyte solutions is presented. The focus is on ion-specific effects as revealed in measurements of osmotic pressure and enthalpy of dilution. We review the experimental results for two different polyelectrolyte systems: (i) salts of polyanetholesulfonic acid, and (ii) aliphatic ionenes (polycations) in aqueous solution with various counterions. A theoretical approach based on the extension of Wertheim's integral equation theory [J. Stat. Phys. 35, 19 (1984)] is used to analyze the experimental data. Preliminary results, based on the all-atom simulation of model 3,3 ionene oligomers, are discussed in the light of polyelectrolyte hydration.

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“…The observed mixing enthalpy was found to be strongly dependent on the nature of the common counterion. Vesnaver et al 60 used the same method for examining the dilution of different PSS salts at various temperatures suggesting that the observed temperature dependence is due to the changes in the water structure in the immediate vicinity of counterions. More recently, Lipar and coworkers 61 measured the enthalpies of dilution for different alkaline salts of polyanetholesulfonic acid.…”

Section: Addition Of +1mentioning

confidence: 99%

Ion-specific and charge effects in counterion binding to poly(styrenesulfonate) anions

Požar

Bohinc

Vlachy

et al. 2011

Phys. Chem. Chem. Phys.

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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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Free enthalpies, enthalpies, and entropies of dilution of aqueous solutions of alkaline earth poly(styrenesulfonates) at different temperatures

Cited by 16 publications

References 0 publications

Counterion-counterion correlation in the double layer around cylindrical polyions: Counterion size and valency effects

Counterion-counterion correlation in the double layer around cylindrical polyions: Counterion size and valency effects

Polyelectrolyte hydration: Theory and experiment

Ion-specific and charge effects in counterion binding to poly(styrenesulfonate) anions

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