CHAPTER 18. Molar Volumes of Electrolyte Solutions

Hefter, Glenn

doi:10.1039/9781782627043-00493

Cited by 10 publications

(43 citation statements)

References 29 publications

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“…Standard state (infinite dilution) values of the volumes and heat capacities, V o and Cp o , for the present salts can in principle be obtained by fitting Y(m) data (Y = V or Cp) with an appropriate theoretical model and extrapolating it to infinite dilution. 29 The most common models used for this purpose are the (extended) Redlich-Rosenfeld-Meyer equation(s) 30,31 and the Pitzer equation(s). 32 Both of these models are semi-empirical but, while they can provide excellent fits of Y(m) data at moderate and high concentrations, it is well known that they do not provide reliable estimates of Y o for 2:2 electrolytes.…”

Section: Standard Molar Valuesmentioning

confidence: 99%

Volumes and Heat Capacities of Cobalt(II), Nickel(II), and Copper(II) Sulfates in Aqueous Solution

et al. 2020

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Densities and isobaric volumetric heat capacities of aqueous solutions of the sulfate salts of cobalt(II), nickel(II) and copper(II) have been measured at 298.15 K and 0.1 MPa using vibrating tube densimetry and Picker flow calorimetry, respectively, at concentrations in the range 0.01 ≲ m/mol•kg -1 ≲ 1.5. These data were used to derive the corresponding apparent molar volumes, V, and apparent molar isobaric heat capacities, Cp.Where comparisons were possible the present V results were in good agreement with literature data. No Cp data appear to have been reported previously for any of these salts. The variations of V and Cp with concentration were well correlated using the Pitzer formalism combined with values of V o and Cp o estimated from literature data. Both V and Cp for all three salts show remarkable similarities and can be shown to lie on a common line by applying fixed addends over almost the whole concentration range studied.

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Section: Standard Molar Valuesmentioning

confidence: 99%

Volumes and Heat Capacities of Cobalt(II), Nickel(II), and Copper(II) Sulfates in Aqueous Solution

et al. 2020

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“…Their V ϕ values are plotted in Figure along with those calculated from the present data for NaOAc(aq) at p = 10 MPa via equation (2) at the same concentration. The two isobars exhibit closely similar shapes but, as expected [8,11], show an increase in V ϕ with increasing pressure and temperature.…”

Section: Comparisons With Literature Datamentioning

confidence: 88%

“…All the numerical values reported in this paper were obtained via equation (2); however, for the convenience of interested users, the experimental data were also fitted with functions of temperature and concentration only. These fits do not yield the proper Debye-Hückel slopes, require more fitting parameters, and are not suitable for extrapolation outside the experimental matrix.…”

Section: Tablementioning

confidence: 99%

“…Theoretical Debye-Hückel slopes, A V , and standard (infinite dilution) partial molar volumes a , V o , at rounded temperatures and p = 10 MPa, calculated via equation (2).…”

Section: Tablementioning

confidence: 99%

“…The volumetric behaviour of aqueous solutions of electrolytes at high temperatures, pressures and concentrations provides important insights into the nature of the solute-solute-solvent interactions in such solutions [1][2][3]. Such information is particularly valuable for salts involving organic ions because they can be used as model systems for the development of functional group additivity models.…”

Section: Introductionmentioning

confidence: 99%

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Apparent molar volumes of aqueous solutions of sodium acetate and sodium benzoate at temperatures from 323 K to 573 K and pressure 10 MPa

Hnědkovský

May

Hefter

2017

The Journal of Chemical Thermodynamics

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Densities of aqueous solutions of sodium acetate and sodium benzoate have been measured at 50 K intervals in the temperature range 323.15 K to 573.15 K at constant pressure p = 10.0 MPa by vibrating tube densimetry. The solute molalities ranged from 0.05 to 4.0 mol•kg-1 (for sodium acetate) or 1.0 mol•kg-1 (for sodium benzoate). The observed densities were used to calculate apparent molar volumes, which were fitted with an extended Redlich-Rosenfeld-Meyer-type equation to yield standard partial molar volumes of the solutes at infinite dilution. No direct comparisons with literature data were possible but the present results are broadly consistent with previous studies. This work greatly expands the database for the volumetric behaviour of both solutes at high temperatures. Despite the probable presence of anion hydrolysis the volumes of both salts show the steep decrease at high temperatures typical of simple 1:1 electrolytes. As expected, the acetate ion has a smaller volume than benzoate, with the difference increasing markedly with temperature, possibly reflecting the greater hydrophobicity of the benzoate ion. Combination of the present results with appropriate literature data enabled calculation of the volume change for the neutralization reaction: HX(aq) + NaOH(aq) → NaX(aq) + H 2 O. The values were similar for the two solutes and show a complex dependence on temperature.

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Thermodynamics of aqueous solutions of ionic liquids composed of [BMPYR] or [BMIM] cations and tetraflate or dicyanamide anions

Havlová

Dohnal

2018

The Journal of Chemical Thermodynamics

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CHAPTER 18. Molar Volumes of Electrolyte Solutions

Cited by 10 publications

References 29 publications

Volumes and Heat Capacities of Cobalt(II), Nickel(II), and Copper(II) Sulfates in Aqueous Solution

Volumes and Heat Capacities of Cobalt(II), Nickel(II), and Copper(II) Sulfates in Aqueous Solution

Apparent molar volumes of aqueous solutions of sodium acetate and sodium benzoate at temperatures from 323 K to 573 K and pressure 10 MPa

Thermodynamics of aqueous solutions of ionic liquids composed of [BMPYR] or [BMIM] cations and tetraflate or dicyanamide anions

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