An equilibrium multicomponent ion exchange model is presented for the ion exchange of group I metals by TAM-5, a hydrous crystalline silicotitanate. On the basis of the data from ion exchange and structure studies, the solid phase is represented as Na3X instead of the usual form of NaX. By using this solid phase representation, the solid can be considered as an ideal phase. A set of model ion exchange reactions is proposed for ion exchange between H+, Na+, K+, Rb+, and Cs+. The equilibrium constants for these reactions were estimated from experiments with simple ion exchange systems. Bromley’s model for activity coefficients of electrolytic solutions was used to account for liquid phase nonideality. Bromley’s model parameters for CsOH at high ionic strength and for NO2- and Al(OH)(4)(-) were estimated in order to apply the model for complex waste simulants. The equilibrium compositions and distribution coefficients of counterions were calculated for complex simulants typical of DOE wastes by solving the equilibrium equations for the model reactions and material balance equations. The predictions match the experimental results within 10% for all of these solutions.