Chemical Modeling of Aqueous Systems II by Daniel C. Melchior, R. L. Bassett

By Daniel C. Melchior, R. L. Bassett

Chemical Modeling in Aqueous platforms

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The WATEQ model actually produced more accurate values than the amended WATEQ model for solutions of O H salts except KOH, for which both models produced inaccurate values. The fit model, by including additional O H complexes, reproduced the experimental data for all O H salts considered. It was possible to estimate parameters for O H complexes of Ba" " , K , Li" ", and N a in the fitting process. Of these complexes, the WATEQ and amended WATEQ models included a O H complex for Ba+ , and the value for the stability constant was similar to that calculated by the fit­ ting process.

For the fit model, aqueous complexes were added as needed in order to resolve the discrepan­ cies between the calculated and experimental mean activity coefficients. The stability constants for the complexes and the individual-ion, activity-coefficient parameters for the complexes were estimated through least-squares fitting. The program that estimated the parameters used the modified version of PHREEQE (10) as a function subroutine that calculated the mean activity coef­ ficient. The stability constants and individual-ion, activity-coefficient parameters of a specified set of complexes were adjusted until a least-squares fit was obtained between the calculated and experimental mean activity coefficients for a series of salt-solution compositions.

Isopiestic, emf, solubility, electrical conductivity, spectroscopic) that are to be explained. Within the framework of the equations given above, one may choose from among different Debye-Huckel submodels, which will also lead to distinct models (see ref. 14 for a review of advances in Debye-Huckel models). In addition, one might modify the equations, for example by including higher-order electrostatic terms (15) or adding empirical virial coefficient terms. Such modifications can be accomplished easily and safely by adding the requisite terms to the equation for the excess Gibbs energy and applying the partial differential equations given earlier in this paper.

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