Determination of osmotic and activity coefficients in mixed electrolyte systems. Systems containing clathrate-forming salts

Wigent, Rodney J.; Leifer, Leslie

doi:10.1021/j150663a048

Cited by 12 publications

(9 citation statements)

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“…The osmotic coefficient for LiCl was accurate to within 0.4% above 2.5 m and 1.2% below 2.5 m, compared to Robinson and Stokes . The osmotic coefficient for TBAC was accurate to within 0.4% above 3.5 m and 1.2% below 3.5 m, compared to Wigent and Leifer …”

Section: Resultsmentioning

confidence: 88%

“…19 The osmotic coefficient for TBAC was accurate to within 0.4% above 3.5 m and 1.2% below 3.5 m, compared to Wigent and Leifer. 4 The average standard deviation in the experimental osmotic coefficient was (0.0030.…”

Section: Resultsmentioning

confidence: 98%

“…There have been relatively few studies on pure and mixed electrolyte solutions containing the clathrate-forming tetraalkylammonium salts, and many interesting thermodynamic properties have been obtained. [1][2][3][4][5] Roy and co-workers 1 have used electromotive force measurements of HBr-n-(C 4 H 9 ) 4 NBr at 25 °C and the Pitzer [6][7][8] equations to determine the thermodynamics of tetrabutylammonium bromide in the mixed system. Wen et al 2 used an isopiestic technique to determine the thermodynamics of tetrapropylammonium bromide in a KBr-Pr 4 NBr-H 2 O solution at 25 °C.…”

Section: Introductionmentioning

confidence: 99%

“…Wen et al 2 used an isopiestic technique to determine the thermodynamics of tetrapropylammonium bromide in a KBr-Pr 4 NBr-H 2 O solution at 25 °C. Padova and co-workers 3 used an isopiestic technique and the Scatchard-Rush [9][10][11][12][13] equations to determine the thermodynamics of the system Pr 4 NCl-NaCl-H 2 O. Wigent and Leifer 4,5 performed an isopiestic analysis of n-(C 4 H 9 ) 4 NCl-NaCl-H 2 O and determined the thermodynamic properties in this system. These studies all indicate that pair, triplet, and higher order multiplet (HOM) interactions play important roles in solutions containing tetraalkylammonium halides.…”

Section: Introductionmentioning

confidence: 99%

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Thermodynamic Studies of Ternary Systems: I. LiCl−(n-Bu)₄NCl−H₂O at 25 °C

Fox

Leifer

2000

J. Phys. Chem. B

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Osmotic coefficients were determined for the ternary system lithium chloride−tetra-n-butylammonium chloride−water over a wide range of concentrations and ionic strength fractions at 25 °C by utilizing a gravimetric isopiestic technique. The mean ionic activity coefficients were calculated using the Scatchard−Rush−Johnson equations. Using the theories developed by Friedman and by Leifer and Wigent, the excess free energy, Friedman's interaction parameters, and contributions due to pairwise, triplet, and quadruplet interactions were determined. The types and relative strengths of ionic interactions in the system containing the hydrophilic lithium ion and hydrophobic tetrabutylammonium ion are discussed.

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Section: Resultsmentioning

confidence: 88%

Section: Resultsmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Thermodynamic Studies of Ternary Systems: I. LiCl−(n-Bu)₄NCl−H₂O at 25 °C

Fox

Leifer

2000

J. Phys. Chem. B

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“…Wigent and Leifer [6] and Leifer and Wigent [7] give equations relating Friedman's g n mixing coefficients to those of Scatchard's neutral-electrolyte model and generalized the mixing terms of the neutral-electrolyte model to include higher-order interactions [7]. Blandamer et al [8] have summarized some additional mixing equations with an emphasis on mixing relations for water activities.…”

Section: Introductionmentioning

confidence: 99%

Conversion of Parameters Among Variants of Scatchard’s Neutral-Electrolyte Model for Electrolyte Mixtures that Have Different Numbers of Mixing Terms

Rard

Wijesinghe

2008

J Solution Chem

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Various model equations are available for representing the excess Gibbs energy properties (osmotic and activity coefficients) of aqueous and other liquid mixedelectrolyte solutions. Scatchard's neutral-electrolyte model is among the simplest of these equations for ternary systems and contains terms that represent both symmetrical and asymmetric deviations from ideal mixing behavior when two single-electrolyte solutions are mixed in different proportions at constant ionic strengths. The usual form of this model allows from zero to six mixing parameters. In this report we present an analytical method for transforming the mixing parameters of neutral-electrolyte-type models with larger numbers of mixing parameters directly to those of models with fewer mixing parameters, without recourse to the source data used for evaluation of the original model that was applied by them to binary systems. It was found that the use of this approach with a constant ionic-strength cutoff of I ≤ 6.2 mol·kg -1 (the NaCl solubility limit) yielded parameters for the NaCl + SrCl 2 + H 2 O and NaCl + MgCl 2 + H 2 O systems that predicted osmotic coefficients φ in excellent agreement with those calculated using the same sets of parameters whose values were evaluated directly from the source data by least-squares, with root mean square differences of RMSE(φ) = 0.00006 to 0.00062 for the first system and RMSE(φ) = 0.00014 to 0.00042 for the second. If, however, the directly evaluated parameters were based on experimental data where the ionic strength cutoff varied with the ionic-strength fraction, i.e. because they were constrained by isopiestic ionic strengths (MgCl 2 + MgSO 4 + H 2 O) or solubility / oversaturation ionic strengths (NaCl + SrCl 2 + H 2 O and NaCl + MgCl 2 + H 2 O), then parameters converted by this approach assuming a 2 constant ionic-strength cutoff yield RMSE(φ) differences about an order of magnitude larger than the previous case. This indicates that for an accurate conversion of model parameters when the source model is constrained with variable ionic strength cutoffs, an extension of the parameter conversion method described herein will be required.However, when the source model parameters are evaluated at a constant ionic strength cuttoff, such as when source isopiestic data are constrained to ionic strengths at or below the solubility limit of the less soluble component, or are Emf measurements that are commonly made at constant ionic strengths, then our method yields accurate converted models.

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Activity coefficients in the system NaCl + Na₂ succinate + H₂O at 25°

Esteso

Fernández-Mérida

Hernández-Luis

et al. 1989

Ber Bunsenges Phys Chem

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Mean ionic activity coefficients of NaCl and Na2Succ (Succ = Succinate ion) in their aqueous mixtures, NaCl + Na2Succ + H2O, were determined at total ionic strengths of 0.5, 1.0, 2.0 and 3.0 mol kg−1, from the emf measurements of galvanic cells. The results obtained were fitted to both the Harned rule and the Pitzer equations. Because the mixture studied is unsymmetrical, the higher‐order electrostatic terms must be taken into account to fit properly the values obtained for this thermodynamic parameter.

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Determination of osmotic and activity coefficients in mixed electrolyte systems. Systems containing clathrate-forming salts

Cited by 12 publications

References 0 publications

Thermodynamic Studies of Ternary Systems: I. LiCl−(n-Bu)₄NCl−H₂O at 25 °C

Thermodynamic Studies of Ternary Systems: I. LiCl−(n-Bu)₄NCl−H₂O at 25 °C

Conversion of Parameters Among Variants of Scatchard’s Neutral-Electrolyte Model for Electrolyte Mixtures that Have Different Numbers of Mixing Terms

Activity coefficients in the system NaCl + Na₂ succinate + H₂O at 25°

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Determination of osmotic and activity coefficients in mixed electrolyte systems. Systems containing clathrate-forming salts

Cited by 12 publications

References 0 publications

Thermodynamic Studies of Ternary Systems: I. LiCl−(n-Bu)4NCl−H2O at 25 °C

Thermodynamic Studies of Ternary Systems: I. LiCl−(n-Bu)4NCl−H2O at 25 °C

Conversion of Parameters Among Variants of Scatchard’s Neutral-Electrolyte Model for Electrolyte Mixtures that Have Different Numbers of Mixing Terms

Activity coefficients in the system NaCl + Na2 succinate + H2O at 25°

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Thermodynamic Studies of Ternary Systems: I. LiCl−(n-Bu)₄NCl−H₂O at 25 °C

Thermodynamic Studies of Ternary Systems: I. LiCl−(n-Bu)₄NCl−H₂O at 25 °C

Activity coefficients in the system NaCl + Na₂ succinate + H₂O at 25°