Ionic Interactions in Aqueous Mixtures of NaCl with Guanidinium Chloride:  Osmotic Coefficients, Densities, Speeds of Sound, Surface Tensions, Viscosities, and the Derived Properties

2000 ◽  
Vol 104 (40) ◽  
pp. 9505-9512 ◽  
Author(s):  
Anil Kumar
Keyword(s):  
Osmotic Coefficients ◽  
Ionic Interactions ◽  
Aqueous Mixtures ◽  
Surface Tensions ◽  
Guanidinium Chloride ◽  
Speeds Of Sound ◽  
Derived Properties

The activity coefficients of elctrolytes with particular reference to aqueous mixtures of 2:2 With 1:1 electrolytes

1971 ◽  
Vol 321 (1547) ◽  
pp. 515-543 ◽  
Keyword(s):  
Exact Solution ◽  
Activity Coefficients ◽  
Infinite Dilution ◽  
Osmotic Coefficients ◽  
Ion Association ◽  
Aqueous Mixtures ◽  
General Application ◽  
Poisson Boltzmann ◽  
High Concentrations ◽  
Charged Ions

Müller’s method for the exact solution of the Poisson-Boltzm an equation (P.B.M.) has been used to produce tables for general application, for the potential, for the activity coefficients and for the osmotic coefficients of 2:2 electrolytes in aqueous solutions, both alone and in the presence of strong 1:1 electrolyte. The activity coefficients for 2:2 electrolytes were found to be equivalent to those derived by Bjerrum ’s method of ionic association up to values of s/a = z 2 e 2 / ϵkTa of about 9. Beyond this value the Poisson-Boltzmann-Müller values of the activity coefficients are significantly higher (about 10% at s/a = 11) and it is shown that the Bjerrum method is better in this range. The P.B.M. calculations show that in the presence of 1:1 electrolyte the Bjerrum treatment of ion association does not give a constant dissociation constant for a 2:2 electrolyte—even at infinite dilution of the latter—and this makes the Bjerrum method less useful when dealing with mixtures of 2:2 and 1:1 electrolytes. The P.B.M. method has been applied to the activity coefficients at CaSO 4 in NaCl solutions (up to 6 mol/1 strength) in the temperature range from 0 to 95 °C ( s/a from 7.85 to 9.05). The results shows very clearly the advantage of using the Kirkwood-Glueckauf approximation rather than the Debye-Hückel term (both in combination with the Müller extension term) when dealing with highly charged ions in solutions of high concentrations.

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