were investigated at atmospheric pressure and T = 303.2 K using the isothermal dissolution equilibrium method. Additionally, solid phase equilibria of the quaternary system Pb 2+ , Mg 2+ , and Ca 2+ //Cl − −H 2 O were determined, and the corresponding stable phase diagrams and density-composition diagrams were constructed. The results indicate that the phase diagrams of Pb 2+ , Ca 2+ //Cl − −H 2 O mainly consist of a ternary invariant point, two solubility curves, and four crystalline regions, while there are two ternary invariant points, three solubility curves, and six crystalline regions in the Pb 2+ , Mg 2+ //Cl − −H 2 O and Ca 2+ , Mg 2+ //Cl − −H 2 O systems. The results of the density-versus-w(CaCl 2 ) plots of the various ternary systems confirm that the density of the equilibrium solution tends to go upward with the increase in the mass fraction of CaCl 2 . The density of various ternary systems reaches the maximum and equilibrium at the corresponding invariant point, and there is no significant change with the further increase in the CaCl 2 mass fraction. Furthermore, the phase diagram of the Pb 2+ , Mg 2+ , Ca 2+ //Cl − −H 2 O quaternary system includes two invariant points, five isothermal dissolution curves, and five crystalline regions. The order of the relative areas of the crystalline regions for the five salts is PbCl