Conductance in electrolyte solutions using the mean spherical approximation

Bernard, Olivier; Kunz, Werner; Turq, Pierre; Blum, L.

doi:10.1021/j100188a049

Cited by 127 publications

(148 citation statements)

References 1 publication

(1 reference statement)

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“…Despite revision of the Fuoss-Onsager treatment [56], doubts remained about the mathematical theory. Later inclusion of higher order terms, solved either empirically [45] or using alternative theoretical treatments [57,58], have improved the range of applicability to approximately c < 1 mol·L −1 . The final step has been taken here, using an empirical approach, to extend the conductance equation to cover the full range of concentrations for which data are available at ambient temperatures.…”

Section: Discussionmentioning

confidence: 99%

The Statistical Description of Precision Conductivity Data for Aqueous Sodium Chloride

Wadsworth¹

2012

J Solution Chem

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Published precise data for NaCl in the temperature range 0-50°C were assembled, corrected to current standards and analyzed by weighted least-squares regression. There was a notable paucity of data at 0°C. Data were analyzed as specific conductivity to avoid violation of the statistical independence assumption. The regression model was a polynomial in √ c, with an added transcendental term. Powers of √ c were added to published equations to extend the range of c fitted. Temperature dependency of the coefficients was individually modeled by cubic functions in the Celsius temperature. Criteria for an acceptable model included lack of bias, similarity to published theoretical equations, and extrapolation to infinite dilution consistent with literature values. The predictive equation chosen was of the form: κ = Λ 0 c − Sc 3/2 + Ec 2 ln c + J 1 c 2 + J 2 c 5/2 + J 3 c 3 + J 4 c 7/2 + J 5 c 4 + J 6 c 9/2 and fit the data without bias but with high precision (±0.33 µS·cm −1 ) for the full range of published concentrations (up to 5.4 mol·L −1 ), over the temperature range 0-50°C, something not previously achieved. All coefficients but J 5 and J 6 were temperature dependent; the latter terms were required for an unbiased fit at higher concentrations (> 1 mol·L −1 ). Solution of the equation for infinite dilution matched published values closely. The use of separate empirical temperature dependency for the equation coefficients may provide an independent means of validating theoretical treatments of conductivity data.

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Section: Discussionmentioning

confidence: 99%

The Statistical Description of Precision Conductivity Data for Aqueous Sodium Chloride

Wadsworth¹

2012

J Solution Chem

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“…(63) in Ref. 22. We reformulated it here with adapted notations, to be able to identify the parameter A.…”

Section: Appendix B: Total Force Applied On the Solutionmentioning

confidence: 99%

Onsager’s reciprocal relations in electrolyte solutions. II. Effect of ionic interactions on electroacoustics

Gourdin-Bertin

Chassagne

Bernard

et al. 2015

The Journal of Chemical Physics

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In electrolyte solutions, an electric potential difference, called the Ionic Vibration Potential (IVP), related to the ionic vibration intensity, is generated by the application of an acoustic wave. Several theories based on a mechanical framework have been proposed over the years to predict the IVP for high ionic strengths, in the case where interactions between ions have to be accounted for. In this paper, it is demonstrated that most of these theories are not consistent with Onsager's reciprocal relations. A new expression for the IVP will be presented that does fulfill the Onsager's reciprocal relations. We obtained this expression by deriving general expressions of the corrective forces describing non-ideal effects in electrolyte solutions. C 2015 AIP Publishing LLC. [http://dx

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“…The impressive feature of this approach is that a simple potential model of charged hard spheres in a continuum can be used for the free ions, which gives analytical results for the transport properties in the framework of the Mean Spherical Approximation for Transport (MSAT) [15,16,33] and of the Associative Mean Spherical Approximation (AMSA) [3-5, 17, 31, 32, 34]. The inclusion of a mass action law (MAL) into the transport theory is also briefly discussed in the appendix.…”

Section: -4mentioning

confidence: 99%

On the influence of molecular structure on the conductivity of electrolyte solutions - sodium nitrate in water

Krienke¹

2013

Condens. Matter Phys.

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Theoretical calculations of the conductivity of sodium nitrate in water are presented and compared with experimental measurements. The method of direct correlation force in the framework of the interionic theory is used for the calculation of transport properties in connection with the associative mean spherical approximation (AMSA). The effective interactions between ions in solutions are derived with the help of Monte Carlo and Molecular Dynamics calculations on the Born-Oppenheimer level. This work is based on earlier theoretical and experimental studies of the structure of concentrated aqueous sodium nitrate solutions.

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Conductance in electrolyte solutions using the mean spherical approximation

Cited by 127 publications

References 1 publication

The Statistical Description of Precision Conductivity Data for Aqueous Sodium Chloride

The Statistical Description of Precision Conductivity Data for Aqueous Sodium Chloride

Onsager’s reciprocal relations in electrolyte solutions. II. Effect of ionic interactions on electroacoustics

On the influence of molecular structure on the conductivity of electrolyte solutions - sodium nitrate in water

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