Mixed Solvent Electrolyte Solutions: A Review and Calculations with the eSAFT-VR Mie Equation of State

[Image: see text] In this work, mixed-solvent mean ionic activity coefficients (MIAC), vapor–liquid equilibrium (VLE), and liquid–liquid equilibrium (LLE) of electrolyte solutions have been addressed. An extended literature review of existing electrolyte activity coefficient models (eG(E)) and electrolyte equations of state (eEoS) for modeling mixed solvent electrolyte systems is first presented, focusing on the details of the models in terms of physical and electrolyte terms, relative static permittivity, and parameterization. The analysis of this literature reveals that the property predictions can be ranked, from the easiest to the most difficult, in the following order: VLE, MIAC, and LLE. We have then used our previously developed eSAFT-VR Mie model to predict MIAC, VLE, and LLE in mixed solvents without fitting any new adjustable parameters. The model was parameterized on MIAC of aqueous electrolyte solutions and successfully extended to nonaqueous, single solvent electrolyte solutions without any new adjustable parameters by using a salt-dependent expression for the relative static permittivity. Our approach yields excellent results for MIAC and VLE of mixed solvent electrolyte solutions, while being fully predictive. LLE is significantly more challenging, and an accurate model for the salt-free solution is crucial for accurate calculations. When the compositions of the two phases in the binary salt-free system are accurately captured, then the electrolyte extension of our model shows a lot of potential and is currently among the best eEoS for LLE prediction in the literature.