Simple electrolytes in the mean spherical approximation

Triolo, R.; Grigera, J. Raúl; Blum, L.

doi:10.1021/j100558a008

Cited by 167 publications

(120 citation statements)

References 5 publications

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“…An important advantage of the MSA is that it can be solved analytically for certain potentials. The MSA has been used to calculate the mean ionic activity coefficients of ionic species in aqueous electrolyte mixtures, and the agreement with experimental data has been shown to be quite good (Triolo et al, 1976;Vericat and Grigera, 1982).…”

Section: Mean Spherical Approximationmentioning

confidence: 88%

“…Blum (1975) and Blum and Hoye (1978) have obtained the solution to the MSA for a multicomponent mixture of charged hard spheres of arbitrary size and charge. This solution has been used by various investigators to evaluate the individual ionic activity coefficients yi of electrolytes (Triolo et al, 1976;Vericat and Grigera, 1982). The logarithm of the ionic activity coefficient is identical to the reduced excess chemical potential over a hard-sphere mixture reference state, pJx/ kT.…”

Section: Mean Spherical Approximationmentioning

confidence: 99%

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Theory of precipitation of protein mixtures by nonionic polymer

Mahadevan

Hall

1992

AIChE Journal

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A theory is developed to predict the solubility of protein mixtures in solutions containing nonionic polymer. Effective protein-protein interactions due to polymer are taken to be volume-exclusion potentials derived using statistical mechanics. Statistical-mechanical perturbation theory is used to calculate chemical potentials. The effects of protein size, mole fraction and polymer concentration on solubility are explored. The theory is extended to include electrostatic interactions. The excess chemical potential of the proteins due to the charges on all species is calculated using the mean spherical approximation for a mixture of charged hard spheres. The theory predicts: the larger protein is preferentially precipitated over the smaller one; the more concentratedprotein is more likely to precipitate; and increasing the charge of a particular protein reduces its ability to precipitate.

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Section: Mean Spherical Approximationmentioning

confidence: 88%

Section: Mean Spherical Approximationmentioning

confidence: 99%

Theory of precipitation of protein mixtures by nonionic polymer

Mahadevan

Hall

1992

AIChE Journal

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“…It seems more than likely that the conclusions drawn here apply also to other less-often-used, semi-empirical electrolyte models such as eNRTL (Song and Chen, 2009), MSA (Triolo et al, 1976), MSA-NRTL (Papaiconomou et al, 2002), UNIQUAC (Iliuta et al, 2002) or the 'mixed solvent electrolyte model' (MSE) implemented by OLI (Wang et al, 2002(Wang et al, , 2004. The temptation to improve the fitting of thermodynamic property models by repeatedly introducing new variants with systemspecific basis functions and additional adjustable parameters is not confined to the Pitzer equations (e.g., see Partanen, 2012).…”

Section: Discussionmentioning

confidence: 77%

Aqueous electrolyte solution modelling: Some limitations of the Pitzer equations

Rowland

Königsberger

Hefter

et al. 2015

Applied Geochemistry

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Despite intense efforts, general thermodynamic modelling of aqueous electrolyte solutions still presents a difficult challenge, with no obvious method of choice. Even though the Pitzer equations seemingly provide a well-established theoretical framework applicable to many chemical systems over a wide range of temperatures and pressures, they are not as widely adopted as their early promise might have suggested. This is strikingly illustrated by the simultaneous appearance in the literature of numerous, different (and potentially incompatible) Pitzer models alongside a proliferation of alternative theoretical approaches with inferior capabilities.To better understand this problem, the ability of the Pitzer equations to represent the physicochemical properties of aqueous solutions has been systematically investigated for exemplar electrolyte systems. Pitzer ion-interaction parameters have been calculated for selected systems by least-squares regression analysis of published solution data for activity coefficients, osmotic coefficients, relative enthalpies, heat capacities, volumes and densities to high temperatures and pressures. Although satisfactory fits can be achieved when the ranges of conditions are carefully chosen and when sufficient data are available to constrain the regression, the fits obtained tend otherwise to be unsatisfactory. The Pitzer equations do not cope well with gaps and other deficiencies in the regressed data. Profound difficulties, poorly recognized hitherto, can also arise because of variation in the sensitivity of the Pitzer functions to values for different physicochemical properties when these are combined. Given the dimensionality of numerous related thermodynamic properties, all changing as functions of composition, temperature and pressure, these problems are difficult to detect, let alone address, especially in multicomponent systems. The growing practice of improving fits simply by adding basis functions (thereby increasing the number of adjustable parameters) should be deprecated because it increases the likelihood of error propagation, introduces subjectivity, makes independent verification difficult and has deleterious implications for both automated data processing and for consistency between thermodynamic models.

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“…This implies that ions are assumed to be pointlike, and that the ionic atmosphere of a given ion has a nonrealistic size at high concentration. The MSA 16 is a linearized approximation theory, like the Debye-Hückel approximation, but it takes into account the size of the ions in describing electrostatic interactions. Therefore, Durand-Vidal proposed to use the MSA to describe the structural properties of ions.…”

Section: B Corrective Forces Proposed In Previous Workmentioning

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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Simple electrolytes in the mean spherical approximation

Cited by 167 publications

References 5 publications

Theory of precipitation of protein mixtures by nonionic polymer

Theory of precipitation of protein mixtures by nonionic polymer

Aqueous electrolyte solution modelling: Some limitations of the Pitzer equations

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

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