Use of Diffusion and Thermodynamic Data to Test the Onsager Reciprocal Relation for Isothermal Diffusion in the System NaCl–KCl–H<sub>2</sub>O at 25°

Dunlop, Peter J.; Gosting, Louis J.

doi:10.1021/j150571a022

Cited by 82 publications

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“…With use of the d(c j 1 ,c j 2 ), H 1 , and H 2 values, the partial molar volumes of solutes 1 and 2 have been computed through the Dunlop-Gosting equation 33 The partial molar volume of solvent, component 0, has been computed from the V h i of the two solutes by the equation:…”

Section: Resultsmentioning

confidence: 99%

Multicomponent Diffusion in Crowded Solutions. 2. Mutual Diffusion in the Ternary System Tetra(ethylene glycol)−NaCl−Water

et al. 2004

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Multicomponent diffusion properties for the tetra(ethylene glycol) (PEG4)-sodium chloride-water ternary system are investigated at constant salt concentration (0.5 mol dm ) and a wide range of PEG4 concentration approaching 3.0 mol dm -3 (60% volume fraction). Cross-velocity correlation (counterflows) for any pair of components in this ternary system is determined. Comparison between the exact multicomponent approach and the pseudobinary approximation, which is based on the assumption that the PEG4-water mixed solvent can be treated as one component, shows how the latter approach is misleading in describing the electrolyte diffusion properties in mixed solvents. Our results show strong coupling between the fluxes of NaCl and PEG4, which is attributed to the NaCl-PEG4 nonpreferential interactions in water. Moreover, the behavior of the NaCl and PEG4 chemical potentials as a function of the system composition can be quantitatiVely extracted from our diffusion measurements with the help of some interesting observations about the viscosity and conductivity properties of the system.

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Section: Resultsmentioning

confidence: 99%

Multicomponent Diffusion in Crowded Solutions. 2. Mutual Diffusion in the Ternary System Tetra(ethylene glycol)−NaCl−Water

et al. 2004

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“…[25][26][27][28][29] The thermodynamics of macromolecule-salt aqueous mixtures is commonly described using molality-based chemical potential derivatives: The preferential interaction coefficient, Γ 12 , is defined by: 7,14 We now show how to relate Γ 12 to the solvent-frame diffusion coefficients. We can first solve eq 5a-d with respect to (L 12 This implies that µ 11 (m) ) 1/m 1 is an excellent approximation for relatively low macromolecule concentrations (≈10 mg/mL).…”

Section: Theorymentioning

confidence: 99%

Determination of Preferential Interaction Parameters by Multicomponent Diffusion. Applications to Poly(ethylene glycol)−Salt−Water Ternary Mixtures

2008

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Poly(ethylene glycol) (PEG) is a hydrophilic nonionic polymer used in many biochemical and pharmaceutical applications. We report the four diffusion coefficients for the PEG-KCl-water ternary system at 25°C using precision Rayleigh interferometry. Here, the molecular weight of PEG is 20 kg mol -1 , which is comparable to that of proteins. The four diffusion coefficients are examined and used to determine thermodynamic preferential interaction coefficients. We find that the PEG preferential hydration in the presence of KCl is 1 order of magnitude larger than that previously obtained under the same conditions for lysozyme, a protein of similar molecular weight. In correspondence, the coupled diffusion in the PEG case was greater than that observed in the lysozyme case. We attribute this difference to the greater exposure of polymer coils to the surrounding fluid compared to that of globular compact proteins. Moreover, we observe that the PEG preferential hydration significantly decreases as salt concentration increases and attribute this behavior to the polymer collapse. Finally, we have also employed the equilibrium isopiestic method to validate the accuracy of the preferential interaction coefficients extracted from the diffusion coefficients. This experimental comparison represents an important contribution to the relation between diffusion and equilibrium thermodynamics.

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“…Thus, thermodynamic analysis on diffusion data is usually performed on (D ij ) 0 . 25 These diffusion parameters are calculated from the measured (D ij ) V by using 21,37 (…”

Section: Thermodynamic Driving Forces For Diffusionmentioning

confidence: 99%

On the Role of Solute Solvation and Excluded-Volume Interactions in Coupled Diffusion

Annunziata

2008

J. Phys. Chem. B

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Coupled diffusion is observed in multicomponent liquid mixtures in which strong thermodynamic interactions occur. This phenomenon is described by cross terms in the matrix of multicomponent diffusion coefficients. This paper reports a theoretical analysis on the relative role of thermodynamic factors and Onsager crosscoefficients on cross-diffusion coefficients relevant to ternary mixtures containing macromolecules or colloidal particles in the presence of salting-out conditions. A new model based on frictional coefficients between solvated solutes is reported. This model predicts that the Onsager cross-coefficient is negative and contributes significantly to cross-diffusion coefficients even at infinite dilution for solutes with a large difference in size. These predictions are consistent with recent experimental results. The role of preferential solvation and excludedvolume interactions on the thermodynamic factors are also examined. Excluded-volume interactions are introduced through the use of the McMillan-Mayer thermodynamic framework after emphasizing some important aspects of diffusion reference frames and thermodynamic driving forces. Finally, new expressions for cross-diffusion coefficients are proposed.

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Use of Diffusion and Thermodynamic Data to Test the Onsager Reciprocal Relation for Isothermal Diffusion in the System NaCl–KCl–H₂O at 25°

Cited by 82 publications

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Multicomponent Diffusion in Crowded Solutions. 2. Mutual Diffusion in the Ternary System Tetra(ethylene glycol)−NaCl−Water

Multicomponent Diffusion in Crowded Solutions. 2. Mutual Diffusion in the Ternary System Tetra(ethylene glycol)−NaCl−Water

Determination of Preferential Interaction Parameters by Multicomponent Diffusion. Applications to Poly(ethylene glycol)−Salt−Water Ternary Mixtures

On the Role of Solute Solvation and Excluded-Volume Interactions in Coupled Diffusion

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Use of Diffusion and Thermodynamic Data to Test the Onsager Reciprocal Relation for Isothermal Diffusion in the System NaCl–KCl–H2O at 25°

Cited by 82 publications

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Multicomponent Diffusion in Crowded Solutions. 2. Mutual Diffusion in the Ternary System Tetra(ethylene glycol)−NaCl−Water

Multicomponent Diffusion in Crowded Solutions. 2. Mutual Diffusion in the Ternary System Tetra(ethylene glycol)−NaCl−Water

Determination of Preferential Interaction Parameters by Multicomponent Diffusion. Applications to Poly(ethylene glycol)−Salt−Water Ternary Mixtures

On the Role of Solute Solvation and Excluded-Volume Interactions in Coupled Diffusion

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Use of Diffusion and Thermodynamic Data to Test the Onsager Reciprocal Relation for Isothermal Diffusion in the System NaCl–KCl–H₂O at 25°