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Extended Specific Ion Theory (ESIT): Theoretical development and application to Harned’s rule

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Abstract

The specific ion theory (SIT) is a convenient ion activity coefficient model that is often used in solubility and solution equilibrium studies. However, its accuracy is limited. The SIT model can be improved by adding higher-order terms, and by allowing cation–cation, and anion–anion interactions. However, extensions of the SIT model tend to lead to a rapidly increasing number of higher-order interaction parameters that need to be known for reliable predictions. Using the analogy of multicomponent extensions of the Redlich–Kister/Margules model, this paper determines how far a virial-type activity coefficient model can be extended before it becomes unmanageable. It was found that a second-order extension of the SIT model is manageable. A first-order model is sufficient to describe Harned’s Rule satisfactorily. It is found that the addition of like-ion interaction parameters (i.e., cation–cation interactions and anion–anion interactions) to the SIT model substantially improves Harned’s Rule calculations, with an error reduction of over 50%. The ion interaction parameters are presented. Like-ion interactions should be interpreted as competitive effects between ion-water interactions rather than direct ion-ion interactions. Using concentration or mole per kg solution (modified molality) as a measure of abundance does not improve the accuracy of a first-order ESIT model but the modified molality scale does improve the accuracy of a 2nd-order ESIT model.

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Harned Coeff SIT.xlsx (Excel file containing the calculation of like-ion interactions in Table 5, as well as Figs. 5 and 6).

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  1. Department of Chemical and Materials Engineering, Gina Cody School of Engineering and Computer Science, Concordia University, Montreal, Quebec, Canada

    Alex De Visscher

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De Visscher, A. Extended Specific Ion Theory (ESIT): Theoretical development and application to Harned’s rule. J Solution Chem 51, 711–733 (2022). https://doi.org/10.1007/s10953-022-01152-4

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