Effect of temperature on the enthalpy of dilution of strong polyelectrolyte solutions

Vesnaver, Gorazd; Rudez, M.; Pohar, C.; Škerjanc, Jože

doi:10.1021/j150655a046

Cited by 34 publications

(49 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: 80%

“…At higher polyelectrolyte concentrations a downward curvature in ⌬H graphs has been noticed, and for 0°C, the heats of dilution of cesium salt of polystyrenesulfonic acid even become endothermic. 39 Note that electrostatic models can only predict for heat to be released upon dilution, as shown in Fig. 2 and also demonstrated by Eq.…”

Section: A Thermodynamic Propertiesmentioning

confidence: 92%

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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: 80%

Section: A Thermodynamic Propertiesmentioning

confidence: 92%

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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“…(3) As expected, these effects become more pronounced with decrease in temperature. This result is in agreement with the previous experimental findings of Vesnaver et al [36] on poly(styrenesulphonic acid) and its alkali metal salts. (4) In all the cases where NaCl, NaBr, or NaI was added to ionene fluoride solutions heat was released upon mixing ( H ITC, T < 0).…”

Section: Calorimetric Resultssupporting

confidence: 94%

“…It was shown that aqueous ionene solutions exhibit strong specific ion effects, where replacing one counterion species by another may yield qualitatively different behaviour of the solution. For example, diluting a solution of 3,3-ionene fluoride with water yields an exothermic effect [26] (in accord with continuum solvent theories [33][34][35][36][37]) but upon addition of water to 3,3-ionene chlorides, bromides, and iodides heat is consumed [26,30]. Furthermore, heat effects upon dilution depend on the hydrophobicity (charge density) of the ionene as well [26,30].…”

Section: Introductionmentioning

confidence: 99%

Thermodynamic analysis of the interaction of partially hydrophobic cationic polyelectrolytes with sodium halide salts in water

et al. 2014

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Isothermal titration calorimetry was used to determine the temperature and concentration dependence of the enthalpy of mixing of 3,3-and 6,6-ionene fluorides, bromides, and iodides with low molecular weight salts (NaF, NaCl, NaBr, and NaI) in water. The magnitudes of the enthalpies, measured in the temperature range from 273 to 318 K, depended on the number of methylene groups on the ionene polyion (hydrophobicity), and on the anion of the added salt (ion-specificity). All enthalpies of mixing of 3,3-and 6,6-ionene fluorides with low molecular weight salts (NaCl, NaBr, and NaI) were negative, which is in contrast to the predictions of standard theories of polyelectrolyte solutions. This fact was interpreted in the light of the ion-water short-range interactions that are not accounted for in those theories. In contrast, the enthalpies of mixing of 3,3-and 6,6-ionene bromides and iodides with NaF were positive, being in accord with theory. Using the calorimetric data, we performed a model thermodynamic analysis of the polyelectrolyte-salt mixing process to obtain changes in the apparent standard Gibbs free energy, enthalpy, entropy, and heat capacity relative to the pure ionene fluorides in water. The results prove that halide ions replace fluoride counterions with a strength increasing in the order chloride < bromide < iodide. The process is enthalpy governed, accompanied by a positive change in the heat capacity.

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“…The ion-specific effects are observable even with strong polyelectrolytes [6]. For cesium poly(styrenesulfonate) at 0°C, for example, even the sign of the enthalpy of dilution is not predicted correctly by popular theories [9]. Examples showing the importance of the ion-specific interaction are given in refs.…”

Section: Introductionmentioning

confidence: 99%

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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Effect of temperature on the enthalpy of dilution of strong polyelectrolyte solutions

Cited by 34 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

Thermodynamic analysis of the interaction of partially hydrophobic cationic polyelectrolytes with sodium halide salts in water

Polyelectrolyte hydration: Theory and experiment

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