Gregory T M, Moreno E C, Patel J M, Brown W E
Institute for Materials Research, National Bureau of Standards, Washington, D.C. 20234.
J Res Natl Bur Stand A Phys Chem. 1974 Nov-Dec;78A(6):667-674. doi: 10.6028/jres.078A.042.
Solubility isotherms of beta-tricalcium phosphate, -Ca(PO), prepared by heating mixtures of CaCO and CaHPO above 800 °C, were determined in the ternary system Ca(OH)-HPO-HO at 5, 15, 25, and 37 °C in the pH range 6.0-7.5 by equilibration with dilute HPO solutions. The results indicate that -Ca(PO) has a negative thermal coefficient of solubility. The solubility product, , was determined as a function of temperature by a generalized least-squares procedure; the resulting equation is the values of and its dispersion at 25 and 37 °C are 1.20(0.056), and 0.283(0.011) × 10. Thermodynamic functions for the dissolution of the salt at the four experimental temperatures are reported. When treated as an adjustable constant, the Ca/P ratio in these -Ca(PO) solutions was found to have the value 1.514(0.010), confirming that the stoichiometry of the high temperature form of this salt is correctly indicated by the above formula. The computed isotherms at 25 °C for several calcium phosphates are compared; it is shown that -Ca(PO) is, next to Ca(PO)OH, the most stable at pH's above 6.36. The singular points of the -Ca(PO) isotherm with those of CaHPO · 2HO and CaHPO are at pH's 5.88 and 6.36, respectively.
通过在800℃以上加热碳酸钙和磷酸氢钙的混合物制备的β-磷酸三钙(β-Ca₃(PO₄)₂)的溶解度等温线,是在5、15、25和37℃下,通过与稀磷酸溶液平衡,在pH范围6.0 - 7.5的Ca(OH)₂-H₃PO₄-H₂O三元体系中测定的。结果表明,β-Ca₃(PO₄)₂具有负的溶解度热系数。通过广义最小二乘法程序确定了溶解度积Ksp作为温度的函数;得到的方程为,在25和37℃下Ksp的值及其分散度分别为1.20(0.056)和0.283(0.011)×10⁻²⁹。报道了该盐在四个实验温度下溶解的热力学函数。当将Ca/P比作为可调常数处理时,发现这些β-Ca₃(PO₄)₂溶液中的Ca/P比为1.514(0.010),证实了该盐高温形式的化学计量由上述公式正确表示。比较了几种磷酸钙在25℃时计算的等温线;结果表明,β-Ca₃(PO₄)₂在pH高于6.36时,仅次于Ca₅(PO₄)₃OH,是最稳定的。β-Ca₃(PO₄)₂等温线的奇点与磷酸氢钙二水合物(CaHPO₄·2H₂O)和磷酸氢钙(CaHPO₄)的奇点分别在pH 5.88和6.36处。