Recalculation of Activity and Osmotic Coefficients of Hydrohalic Acids and Some Alkali Metal Halides in Dilute Aqueous Solutions at 298.15 K.

Partanen, Jaakko I.; Britz, Dieter; Skrydstrup, Troels; Karinen, Reetta; Sjöstróm, Michael; Wold, Svante; Berglind, Rune; Karlsson, Britt

doi:10.3891/acta.chem.scand.45-0993

Cited by 11 publications

(20 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Moreover, the effect of ionic strength on mixing behavior is negligible or close to it, in line with much evidence that at higher concentrations Harned coefficients become less dependent on concentration . We also note, incidentally, that the experimental data at 0.1 are not matched using the author’s tabulated parameters and that their value of γ KBr pure (in their Table ) is 0.934 at 0.0052 mol·kg –1 compared to literature values of 0.926 or 0.927. − …”

Section: Resultssupporting

confidence: 81%

An Investigation of Harned’s Rule for Predicting the Activity Coefficients of Strong Aqueous Electrolyte Solution Mixtures at 25 °C

Rowland

May

2016

J. Chem. Eng. Data

View full text Add to dashboard Cite

From a critical evaluation of the relevant literature, Harned coefficients at 25 °C and their corresponding trace activity coefficients are reported for 72 mixtures of strong aqueous electrolytes with a common ion. The work confirms the generality of Harned’s rule in its simplest form, that is, with only one (linear) term. Uncertainties in predicted mean activity coefficients are typically less than 0.01, comparable with the experimental reproducibility. Unless there are good grounds to suggest that significant changes in chemical speciation are occurring, experimental measurements that do not conform to the rule should be regarded with suspicion. We find that the estimates of errors made by authors of single potentiometric investigations are often as much as an order of magnitude too optimistic. Even the work of Harned and colleagues, which was typically of high quality, is sometimes much worse than is claimed or implied in the literature. The unfortunately common practice of introducing a quadratic term (as a second adjustable parameter) to extend Harned’s rule is unjustified, within the true current limits of experimental error. Harned’s rule with just one coefficient provides a description of aqueous strong electrolyte mixing thermodynamics which is widely applicable, satisfactorily accurate, and without sign of any systematic problem.

show abstract

Section: Resultssupporting

confidence: 81%

An Investigation of Harned’s Rule for Predicting the Activity Coefficients of Strong Aqueous Electrolyte Solution Mixtures at 25 °C

Rowland

May

2016

J. Chem. Eng. Data

View full text Add to dashboard Cite

show abstract

“…where the Debye-Hückel parameter A has a value of 0.5108 (mol Á kg À1 ) À1/2 [=a/ln (10)]. The parameter values of these equations for alkali metal nitrates are shown in table 1.…”

Section: Theorymentioning

confidence: 98%

“…Theoretically, this model is connected to the ionic hydration theory of Stokes and Robinson [9] in reference [10]. The values of B and b 1 for LiNO 3 , NaNO 3 , and KNO 3 in dilute solutions were determined here from the isopiestic data measured by Robinson [3] and for RbNO 3 and CsNO 3 from the reported osmotic coefficients of Robinson [5].…”

Section: Introductionmentioning

confidence: 99%

Re-evaluation of the thermodynamic activity quantities in aqueous alkali metal nitrate solutions at T= 298.15 K

Partanen

2010

The Journal of Chemical Thermodynamics

View full text Add to dashboard Cite

“…b G is a parameter associated with the ion-size parameter a* by the equation b G ) βa* where β ) 3.245 (mol kg -1 ) -1/2 nm -1 . In the present calculations a value of b G ) 1.25 (mol kg -1 ) -1/2 was used for all ions existing in phthalate solutions, and this value has been determined for HCl solutions in the previous papers (Partanen 1989(Partanen , 1991. In the original Guggenheim method a value of b G ) 1.0 (mol kg -1 ) -!/2 was used (Guggenheim and Turgeon, 1955;Lewis et al, 1961).…”

Section: Results Of Calculationsmentioning

confidence: 99%

“…Estimation of Parameters for Guggenheim Method. The following parameter values for eqs 1-4 were taken from the literature: b G ) 1.25 (mol kg -1 ) -1/2 , β G,HCl ) 0.38, and β G,KCl ) 0.06 (Partanen, 1989(Partanen, , 1991. Parameter β G,KHPh in eq 3 was estimated from sets HPA45I-V in Table 1 by means of the following equation derived similarly as eq 25:…”

Section: Pt(s) Ormentioning

confidence: 99%

Equations for the Calculation of the pH of Buffer Solutions Containing Potassium Hydrogen Phthalate, Dipotassium Phthalate, and Potassium Chloride at 298.15 K

Partanen

Minkkinen

1997

J. Chem. Eng. Data

View full text Add to dashboard Cite

Published experimental thermodynamic data at 298.15 K for aqueous mixtures of H2Ph, KHPh, and KCl, of KHPh, K2Ph, and KCl, and of KHPh and KCl, where H2Ph means phthalic acid, KHPh potassium hydrogen phthalate, and K2Ph dipotassium phthalate, were used to test the methods for calculation of the pH values of phthalate buffer solutions. Equations for ionic activity coefficients are used in these methods. It is shown that all data used, up to an ionic strength of about 0.5 mol kg-1, can be predicted almost within experimental error by two methods. In one of these methods, equations of the modified Guggenheim type are used for ionic activity coefficients, and in the other equations of the Pitzer type are used. Several sets of phthalate buffer solutions are suggested in the pH range 3.8−5.3, e.g., for calibration solutions for glass electrode cells or for constant-pH reaction media where the pH is known. In the recommended sets, the pH values of the buffer solutions have been calculated by the Guggenheim method, and the pH predictions of the Pitzer method agree with those in most cases within 0.01 at least up to ionic strengths of about 0.15 mol kg-1. The recommended pH = 4.005 of the standard reference solution (0.05 mol kg-1 KHPh solution) agrees closely with the value suggested in the present study (4.003) for this solution.

show abstract

Recalculation of Activity and Osmotic Coefficients of Hydrohalic Acids and Some Alkali Metal Halides in Dilute Aqueous Solutions at 298.15 K.

Cited by 11 publications

References 0 publications

An Investigation of Harned’s Rule for Predicting the Activity Coefficients of Strong Aqueous Electrolyte Solution Mixtures at 25 °C

An Investigation of Harned’s Rule for Predicting the Activity Coefficients of Strong Aqueous Electrolyte Solution Mixtures at 25 °C

Re-evaluation of the thermodynamic activity quantities in aqueous alkali metal nitrate solutions at T= 298.15 K

Equations for the Calculation of the pH of Buffer Solutions Containing Potassium Hydrogen Phthalate, Dipotassium Phthalate, and Potassium Chloride at 298.15 K

Contact Info

Product

Resources

About