Electrolyte solutions, thermodynamics Debye-Huckel parameters

In this appendix, we summarize the coefficients needed to calculate the thermodynamic properties for a number of solutes in an electrolyte solution from Pitzer s equations.3 Table A7.1 summarizes the Debye-Huckel parameters for water solutions as a function of temperature. They provide the leading terms for Pitzer s equations, and can also be used to calculate the Debye-Huckel limiting law values from the equations... 

This standard textbook on chemical thermodynamics contains an Appendix (no. 4) of selected data for aqueous electrolyte solutions. Compiled are activity coefficients, Debye-Huckel parameters, relative partial molar enthalpies, and relative partial molar heat capacities for about 70 of the most common electrolytes in aqueous solution at 25 °C. More recent Debye-HUckel parameters are to be found 1n the pages of Pitaer, Pelper, and Busey and of Bradley and Pitaer (see item [121]) and the paper of Clarke and Glew, Hem [223. 

The tables in this chapter include Debye-HUckel parameters for the osmotic coefficient, enthalpy, and heat capacity as a function of temperature parameters for the activity and osmotic coefficients of approximately 270 aqueous strong electrolytes at 25 C parameters for the relative apparent molar and excess enthalpy of %90 strong electrolytes at 25 C a table of parameters for the activity and osmotic coefficients ofss75 binary mixtures with and without common ions and with up to three solutes present and parameters for the thermodynamic properties of aqueous NaCI and H2SO4 as a function of temperature. The author has included references to his earlier papers ivhich also contain valuable data on electrolyte solutions (also see item [121]). 

Some other kinds of models have shown parameters that seem to follow useful correlation relationships. Among these are the virial coefficient model of Bums (2), the interaction coefficient model of Helgeson, Kirkham, and Flowers (4), and the hydration theory model of Stokes and Robinson (1). The problem shared by all three of these models is that they employ individual ion size parameters in the Debye-Hiickel submodel. This led to restricted applicability to solutions of pure aqueous electrolytes, or thermodynamic inconsistencies in applications to electrolyte mixtures. Wolery and Jackson (in prep.) discuss empirical modification of the Debye-Huckel model to allow ion-size mixing without introducing thermodynamic inconsistencies. It appears worthwhile to examine what might be gained by modifying these other models. This paper looks at the hydration tlieory approach. 

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