The effect of concentration- and temperature-dependent dielectric constant on the activity coefficient of NaCl electrolyte solutions

Valiskó, Mónika; Boda, Dezső

doi:10.1063/1.4883742

Cited by 66 publications

(82 citation statements)

References 84 publications

(135 reference statements)

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“…For NaCl, a detailed analyzis on the sensitivity of our theory on the model parameters has been published [101]. For NaBr, interestingly, the data of VWV agree with those of Hurlen, but both are different from other measurements (Lee et al [124] and Zhuo et al [44]; they agree with each other well).…”

Section: Resultssupporting

confidence: 51%

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Unraveling the Behavior of the Individual Ionic Activity Coefficients on the Basis of the Balance of Ion–Ion and Ion–Water Interactions

Valiskó

Boda

2015

J. Phys. Chem. B

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We investigate the individual activity coefficients of pure 1:1 and 2:1 electrolytes using our theory that is based on the competition of ion-ion (II) and ion-water (IW) interactions (Vincze et al., J. Chem. Phys. 133, 154507, 2010). The II term is computed from Grand Canonical Monte Carlo simulations on the basis of the implicit solvent model of electrolytes using hard sphere ions with Pauling radii. The IW term is computed on the basis of Born's treatment of solvation using experimental hydration free energies. The two terms are coupled through the concentration-dependent dielectric constant of the electrolyte. With this approach we are able to reproduce the nonmonotonic concentration dependence of the mean activity coefficient of pure electrolytes qualitatively without using adjustable parameters. In this paper, we show that the theory can provide valuable insight into the behavior of individual activity coefficients too. We compare our theoretical predictions against experimental data measured by electrochemical cells containing ion-specific electrodes. As in the case of the mean activity coefficients, we find good agreement for 2:1 electrolytes, while the accuracy of our model is worse for 1:1 systems. This deviation in accuracy is explained by the fact that the two competing terms (II and IW) are much larger in the 2:1 case so errors in the two separate terms have less effects. The difference of the excess chemical potentials of cations and anions (the ratio of activity coefficients) is determined by asymmetries in the properties of the two ions: charge, radius, and hydration free energies.

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Section: Resultssupporting

confidence: 51%

“…In our previous works [104,105,101], we have introduced the II+IW model in which the excess chemical potential is split into two terms…”

mentioning

confidence: 99%

Unraveling the Behavior of the Individual Ionic Activity Coefficients on the Basis of the Balance of Ion–Ion and Ion–Water Interactions

Valiskó

Boda

2015

J. Phys. Chem. B

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“…The classical Born solvation model uses the continuum solvent, so it cannot give the 23802-7 necessary molecular description. Born models are still useful though, a fairly recent example being the use of simulated PM results with a Born description of the ion-water interaction [35].…”

Section: -6mentioning

confidence: 99%

Thermodynamics of primitive model electrolytes in the symmetric and modified Poisson-Boltzmann theories. A comparative study with Monte Carlo simulations

Quiñones¹,

Bhuiyan²,

Outhwaite³

2018

Condens. Matter Phys.

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Osmotic coefficients, individual and mean activity coefficients of primitive model electrolyte solutions are computed at different molar concentrations using the symmetric Poisson-Boltzmann and modified Poisson-Boltzmann theories. The theoretical results are compared with an extensive series of Monte Carlo simulation data obtained by Abbas et al. [Fluid Phase Equilib., 2007, 260, 233; J. Phys. Chem. B, 2009, 113, 5905]. The agreement between modified Poisson-Boltzmann predictions with the "exact " simulation results is almost quantitative for monovalent salts, while being semi-quantitative or better for higher and multivalent salts. The symmetric Poisson-Boltzmann results, on the other hand, are very good for monovalent systems but tend to deviate at higher concentrations and/or for multi-valent systems. Some recent experimental values for activity coefficients of HCl solution (individual and mean activities) and NaCl solution (mean activity only) have also been compared with the symmetric and modified Poisson-Boltzmann theories, and with the Monte Carlo simulations.

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“…where R i is the radius of ionic species i, 0 is the permittivity of vacuum, and r is the distance between the ions. The radius is the Pauling radius in this work, although other choices are also possible [23]. The Pauling radii and other data are collected in Table 1.…”

Section: Calculation Of the II Termmentioning

confidence: 99%

“…A few notable exceptions are the papers of Abbas et al [5] and Inchekel et al [20]. In 2010, we proposed the II+IW theory [21][22][23][24][25] in which we split the excess chemical potential into two components…”

Section: Introductionmentioning

confidence: 99%

Activity coefficients of individual ions in LaCl₃from the II+IW theory

Valiskó

Boda

2017

Molecular Physics

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We investigate the individual activity coefficients of ions in LaCl3 using our theory that is based on the competition of ion-ion (II) and ion-water (IW) interactions (Vincze et al., J. Chem. Phys. 133, 154507, 2010). The II term is computed from Grand Canonical Monte Carlo simulations on the basis of the implicit solvent model of electrolytes using hard sphere ions with Pauling radii. The IW term is computed on the basis of Born's treatment of solvation using experimental hydration free energies.The results show good agreement with experimental data for La 3+ . This agreement is remarkable considering the facts that (i) the result is the balance of two terms that are large in absolute value (up to 20kT ) but opposite in sign , and (ii) that our model does not contain any adjustable parameter.All the parameters used in the model are taken from experiments: concentration dependent dielectric constant, hydration free energies, Pauling radii.

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The effect of concentration- and temperature-dependent dielectric constant on the activity coefficient of NaCl electrolyte solutions

Cited by 66 publications

References 84 publications

Unraveling the Behavior of the Individual Ionic Activity Coefficients on the Basis of the Balance of Ion–Ion and Ion–Water Interactions

Unraveling the Behavior of the Individual Ionic Activity Coefficients on the Basis of the Balance of Ion–Ion and Ion–Water Interactions

Thermodynamics of primitive model electrolytes in the symmetric and modified Poisson-Boltzmann theories. A comparative study with Monte Carlo simulations

Activity coefficients of individual ions in LaCl₃from the II+IW theory

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The effect of concentration- and temperature-dependent dielectric constant on the activity coefficient of NaCl electrolyte solutions

Cited by 66 publications

References 84 publications

Unraveling the Behavior of the Individual Ionic Activity Coefficients on the Basis of the Balance of Ion–Ion and Ion–Water Interactions

Unraveling the Behavior of the Individual Ionic Activity Coefficients on the Basis of the Balance of Ion–Ion and Ion–Water Interactions

Thermodynamics of primitive model electrolytes in the symmetric and modified Poisson-Boltzmann theories. A comparative study with Monte Carlo simulations

Activity coefficients of individual ions in LaCl3from the II+IW theory

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Activity coefficients of individual ions in LaCl₃from the II+IW theory