Simultaneous equilibrium was applied to the thermodynamic analysis and calculation of Bi（Ⅲ）-X（Cl-, NO-3）-H2O systems, based on which the diagrams of the logarithm of equilibrium concentration of Bi（Ⅲ） of series precipitation vs pH value of these two systems at 25 ℃ were obtained, and the pH ranges of the stable zones of various precipitations were analyzed and determined. In Bi（Ⅲ）-Cl--H2O system, the variations of c0(Bi3+) and （c0（Cl-）） have little effect on the equilibria of Bi（OH）3-solution and BiOOH-solution, but has great influence on the （equilibrium） of BiOCl-solution. However, in Bi（Ⅲ）-NO-3-H2O system, the variations of c0(Bi3+) and c0（NO-3） have little effect on equilibria of Bi（OH）3-solution, BiOOH-solution and Bi2O3-solution. When pH value is high, Bi2O3 is the thermodynamic stable phase, its stable zone is the widest, almost including the stable zones of BiOCl or （BiONO3,） （Bi（OH）3） and BiOOH. Bi（OH）3 cannot be obtained from Bi（Ⅲ）-Cl--H2O system, even strong alkaline media. Bi2O3 can be obtained from the solution directly, and highly pure BiOCl or BiONO3 can also be obtained through strictly controlling pH value.
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