The solubility isoth erm for CaHP04 • 2H,O (DCPD) in the three-component system Ca(OH), -H3P04 -H,O was determined in the pH range 3.5 to 6.8 by leaching a thermostated column of DCPD with dilute phosphoric acid solutions. In confirmatory experiments, equilibrium was approached both from s uper-and under-saturation by shakin g DCPD with appropriate solutions. The calcu lated ioni c activity product (Ca + +) X (HPO ,), appeared to be a parabolic function of pH with a minimum near pH 5.0. The pH dependence of the ionic product could be accounted for by co nsid erin g th e ion pairs [CaHP04] O and [CaH,P04]+ as semi-empirical parameters, Under the co ndition of saturation with respect to DCPO , the activity of the pair [CaHPO,]O mu st be a consta nt. The act iv ity of th e species [CaH,PO,]+ was shown to vary direc tl y with hydrogen ion activity. The activiti es of the two ion pairs were adjusted to give a set of pH-independen t ionic activit y produ cts with a mean of 2.19 ± 0.011 X 10 -'. The stabilit y consta nts for [CaHP04]0 a nd [CaH,PO,] + are 5.88 ± 0.031 X 10' and 7.49 ± 0.039, respectively. Experiments were conducted to study the hydrolysis of DCPD to more basic calcium phosphates and the kin etics of these transformations is discussed. The significance of the ion pairs in hum an se rum is co nsidered.Key Words : Solubilit y of calcium monohydroge n ph osp hate dihydrate at 37.5 °C, calciumph os phate ion-pairs, solubility of di calcium phosphate dih ydrate , so lubilit y of dibasic calc ium phosphate dihydrate .