The mechanisms of transperitoneal potassium transport during peritoneal dialysis were evaluated by validation of different mathematical models. The models were designed to elucidate the presence or absence of diffusive, non-lymphatic convective and lymphatic convective solute transport. Experimental results were obtained from 26 non-diabetic patients undergoing peritoneal dialysis. The validation procedure demonstrated that models including both diffusive and non-lymphatic convective solute transport were superior to the other models. Lymphatic convective solute transport was not identifiable. Furthermore, it was demonstrated experimentally that the equilibrium distribution of potassium between plasma water and dialysate did not differ from a Donnan equilibrium, although the precondition of the Donnan equilibrium was not fulfilled, i.e. the volumes on each side of the membrane were not constant and dialysate was not an ultrafiltrate of plasma.