Abstract A new model for representation of the excess Gibbs energy of electrolyte solutions is proposed. The excess Gibbs energy of an electrolyte solution is expressed as a sum of contributions of a long-range and a short-range excess Gibbs energy term. The Pitzer–Debye–H¨uckel model is used as a long-range contribution to the excess Gibbs energy. A new expression based on the local composition concept, which is the non-random factor (NRF)–Wilson model, is developed to account for the short-range contribution to the excess Gibbs energy. The main difference between this model and the electrolyte-NRF model available in the literature is the assumption that the short-range energy parameter between species in a local cell has an enthalpic rather than Gibbs energy nature. The utility of the model is demonstrated with the successful representation of the mean ionic activity coefficient of several aqueous electrolyte solutions. The results show that with only two adjustable parameters per electrolyte, the model is valid for the whole range of electrolyte concentration, from dilute solution up to saturation. The results are compared with those obtained from the NRTL, NRF and Wilson models. The model presented in this work produces better results.
