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The design and optimization of solvent extraction processes for metal separations are challenging tasks due to the large number of adjustable parameters. A quantitative predictive solvent extraction model could help to determine the optimal parameters for solvent extraction flow sheets, but such predictive models are not available yet. The main difficulties for such models are the large deviations from ideal thermodynamic behavior in both the aqueous and organic phases due to high solute concentrations. We constructed a molecular thermodynamic model for the extraction of CoCl 2 from different chloride salts by 0.2 mol L -1 rioctylmethylammonium chloride in toluene using the OLI mixed-solvent electrolyte (OLI-MSE) framework. This was accomplished by analyzing the water and hydrochloric acid content of the organic phase, measuring the water activity of the system, and using metal complex speciation and solvent extraction data. The full extractant concentration range cannot be modeled by the OLI-MSE framework as this framework lacks a description for reversed micelle formation. Nevertheless, salting effects and the behavior of hydrochloric acid can be accurately described with the presented extraction model, without determining specific Co(II)-salt cation interaction parameters. The resulting model shows that the salting effects originate from indirect salt cation-solvent interactions that influence the availability of water in the aqueous and organic phases.

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Thermodynamic Modeling of Salting Effects in Solvent Extraction of Cobalt(II) from Chloride Media by the Basic Extractant Methyltrioctylammonium Chloride