Untitled

Hu, Yu‐Feng; Fan, Shuanshi

doi:10.1023/a:1011940327109

Cited by 8 publications

(1 citation statement)

References 18 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This approximate relationship was first discovered empirically by Zdanovskii and later derived independently by Stokes and Robinson . Some of the underlying theory has been reviewed by Frolov, and other recent studies include a number of practical applications. − The ZSR relationship has also been applied to the estimation of volumetric and thermal properties of mixtures, , the speed of sound, and freezing point depression . In addition to the expression for solvent content, corresponding ZSR equations exist for solute activity coefficients, and the method has been extended to include ternary (two solute, single solvent) mixture parameters whose values are determined from experimental data. − Clegg et al have demonstrated the application of the extended model to reciprocal salt and other systems, and have also derived expressions for cases in which a subset of solutes within a mixture have their osmotic and activity coefficients described by some other model within the overall ZSR expression.…”

Section: Introductionmentioning

confidence: 99%

Improvement of the Zdanovskii−Stokes−Robinson Model for Mixtures Containing Solutes of Different Charge Types

Clegg

Seinfeld

2004

J. Phys. Chem. A

View full text Add to dashboard Cite

The Zdanovskii−Stokes−Robinson (ZSR) relationship [Stokes and Robinson (J. Phys. Chem. 1966, 70, 2126−2130)] enables the solvent content of a liquid mixture to be estimated, for a specified solvent activity, from data for pure solutions of each of the individual solutes. There is an analogous relationship for the activity coefficients of the solutes. The method has been shown to be exact, in the limit of extreme dilution, only for mixtures containing either all uncharged (neutral) solutes or electrolytes all of the same charge type, and in practice it is found to be most accurate for such mixtures. Here we derive an addition to the ZSR equations which removes this limitation by incorporating simple Debye−Hückel terms into the equations for solvent mass and solute activity coefficients. This addition, in its simplest form, does not involve any new fitted parameters or require any further thermodynamic information. The relationship is general, and not limited to particular Debye−Hückel expressions. Application of the revised model to activity and osmotic coefficient data for the system NaCl−Na2SO4−H2O at 298.15 K shows that errors are reduced, compared to predictions of the standard model, by up to a factor of 2. Solubilities of NaCl(cr), Na2SO4·10H2O(cr), and Na2SO4(cr) in that system are similarly better predicted. Activity coefficients of uncharged solutes in salt solutions calculated using the revised model are now largely consistent with the empirically observed Setchenow relationship.

show abstract