The ternary and quaternary electrolyte systems: Activity coefficient of NaCl measured and modeled for NaCl + C2H5OH + H2O and NaCl + KCl + C2H5OH + H2O systems

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This article focuses on measuring and modeling activity coefficients and some thermodynamic properties of the quaternary system (NaCl + KCl + N,N-dimethylformamide (DMF) + H 2 O) using a potentiometric technique at (298.15 ± 0.05) K. By employing ion-selective electrodes (Na + -ISE, Cl − -ISE), experimental results were collated for the four series of the mixed electrolyte systems in various ionic strengths for the investigated quaternary system. The electrochemical measurements were carried out over total ionic strengths range from 0.0249 up to about 3.8223 mol•kg −1 in mixed N,N-dimethylformamide + H 2 O solvents, with various solvent mass percents (wt % = 0.0, 0.10, 0.20, and 0.30) at 298.15 ± 0.05 K. Experimental data were modeled on the basis of the Pitzer approach, and the two and three particles mixing ionic interaction parameters (θ NaK and ψ NaKCl ) estimated for the quaternary electrolyte systems under investigation. Finally, using the optimized parameters (θ NaK and ψ NaKCl ), the thermodynamic properties of electrolyte systems, such as activity coefficients of the constituent's electrolyte, osmotic coefficients, and the excess Gibbs free energy, were determined for each mass percent of DMF in water for mixtures of sodium and potassium salts with common anion chloride. The resultant activity coefficients demonstrate a decreasing trend upon decreasing dielectric constants and as the mixed solvent medium growing dense and viscous.

Section: Introductionmentioning

confidence: 99%

Quaternary System Thermodynamic Investigation in a Mixed Solvent: NaCl + KCl + N,N-Dimethylformamide + H₂O

Masumi

Salamat-Ahangari

2021

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“…Measuring and modeling for electrolyte behavior in aqueous and nonaqueous media is necessary because of the need to investigate the nature of various industrial and environmental processes. Despite the successful achievements of mixed electrolyte studies in aqueous media, investigations in nonaqueous or in mixed solvent media are still very limited. − Among the proposed equations, the Pitzer model and the Harned rule seemed to be the most favored ones among the published works. Typically some of the literature used the Harned rule, − while the others implemented the Pitzer formalism. − …”

Section: Introductionmentioning

confidence: 99%

Mixed Electrolyte in Mixed Solvent: Activity Coefficient Measuring and Modeling for the HCl + NaCl + Methanol + Water System

Karimzadeh

Hosseini

2019

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The emf of the cell is measured to investigate the HCl + NaCl + H2O + CH3OH mixed electrolyte systems. The experimental data are obtained over the electrolyte molality ranging from 0.005 mol kg–1 up to about 3.5 mol kg–1, at 298.15 ± 0.01 K, by using a cell containing a pH and a silver chloride electrode in different alcohol mass fractions x(CH3OH) in H2O (where x = 0.10, 0.20, 0.30, 0.40, and 0.50). The mean activity coefficients of HCl in the mixtures are computed. Modeling is implemented by the classical Pitzer (CP) equation and original Pitzer (OP) equation that are included by the additional terms which are arising from interactions of neutral species and finally the modified Pitzer equation by Merida et al. (MP). The different aspects of proper parameter choosing in fitting processes especially for pure and mixed electrolytes in mixed solvent systems are signified in the results.

“…27−41 Our group has lately made use of the potentiometric method and Pitzer ion interaction and the modified Pitzer approaches to determine and describe the interactions between nonelectrolyte (amide, carbohydrate, and alcohols) and inorganic salts in multicomponent solutions, namely, the ternary and quaternary systems of mixed electrolytes (NaCl+KCl) in mixed solvents (such as N,N-dimethylformamide + water) and in aqueous alcohol solutions. 36,40,41 As continuation of our studies on the binary mixed electrolytes in binary mixed solvents, a survey of literature indicates that the thermodynamic data of mixed salts of sodium and rubidium chlorides in a mixed CH 3 OH + H 2 O system have not been reported to date. Taking into account the considerations quoted above, the main objective of this study is the measuring and modeling of the activity coefficients of the electrolytes and subsequently osmotic coefficients and Gibbs free energies in a quaternary system (NaCl + RbCl + CH 3 OH + H 2 O) by using the electromotive force measurement technique.…”

Section: Introductionmentioning

confidence: 71%

Thermodynamic Study of Binary Sodium Chloride and Rubidium Chloride in Mixed Methanol–Water Employing the EMF Method

Abbasi Rostami,

Salamat-Ahangari

2024

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This article reports the results of thermodynamic modeling of activity and osmotic coefficients of the quaternary system of mixed NaCl + RbCl in mixed CH3OH + H2O solvent based on the potentiometric method at 298.15 ± 0.05 K. By employing the EMF method without the liquid junction comprising chloride-selective and sodium-selective electrodes, the measurements were accomplished over the concentration range from 0.0005 up to 2.4941 mol·kg–1 for different series of salt molal ratios (r = m NaCl/m RbCl = 100, 150, 200, and 250) with various alcohol mass percentages in water (w = 0.0, 0.10, 0.20, 0.30, and 0.40). The experimental results were modeled and interpreted in terms of the Pitzer ion-interaction approach. Exploiting the Pitzer model permitted the optimization and determination of the unknown Pitzer mixing parameters (θNaRb and ψNaRbCl) for each series of the investigated system. Eventually, having evaluated these parameters of the Pitzer model, it was possible to compute the activity coefficients of the constituent’s electrolyte, the excess Gibbs energy, and osmotic coefficients for various fractions of methanol in water for mixtures of sodium and rubidium electrolytes with common anion. The results of modeling for the system under consideration were surprisingly in good agreement with an empirical rule by Harned for the second electrolyte.