Electrochemical membrane technologies such as electrodialysis have been identified as key technologies to enable nutrient recovery from wastewater. However, current electrochemical models are focused on simpler solutions than wastewater and omit key outputs such as pH, or total cell potential. A combined physico-chemical and electrochemical model was developed which includes the mechanisms of competitive transport of ions, implicit inclusion of H(+) and OH(-), pH (including ionic activity and ion pairing), different factors contributing to total cell potential and a novel method for ion exchange membrane transport. The model outputs compare well with measurements from experiments and simulate secondary effects such as electrode reactions and current leakage. Results found that membrane, rather than boundary layer or bulk resistance was the major contributor to potential drop, and that apparent boundary layers were relatively thick (3 ± 1 mm). Non-ideal solution effects such as ion-pairing and ionic activity had a major impact, particularly on multi-valent Ca(2+) ions, which enhances the capability of electrodialysis to recover monovalent nutrient ions such as K(+) and NH4(+). Decreased resistivity of ion exchange membranes to specific ions (for example, in this case nitrate) could also be detected. The methods here are validated using a comparatively simple synthetic solution of five ionic components, but are able to be easily scaled for a more complex solution, and are also compatible with additional mechanisms such as precipitation, fouling, and scaling.