Solubility and Stability of Calcium Arsenates at 25∘C

Abstract

The solubility and stability of calcium arsenates at 25 ∘C was determined by both precipitation and dissolution experiments. Ca3(AsO4)2⋅ 3H2O(c), Ca3(AsO4)2⋅ 21/4H2O(c), Ca5(AsO4)3(OH)(c) and Ca4(OH)2(AsO4)2⋅ 4H2O(c) were identified in our experiment over a wide range of pH and for Ca/As molar ratios between 1.25 and 4.0. The solids precipitated at pH = 3 ∼ 7 and Ca/As = 1.5 were phase-pure and well-crystallized Ca3(AsO4)2⋅ xH2O(c) and had relatively larger grain size than those formed at pH > 7. Based on the analytical results and using the computer program PHREEQC, the solubility products for Ca3(AsO4)2⋅ 3H2O(c), Ca3(AsO4)2⋅ 21/4H2O(c), Ca5(AsO4)3(OH)(c) and Ca4(OH)2(AsO4)2⋅ 4H2O(c) were calculated as Ksp of 10− 21.14(10− 20.01 ∼ 10− 22.02), 10− 21.40(10− 20.08 ∼ 10− 21.98), 10− 40.12(10− 37.53 ∼ 10− 42.72) and 10− 27.49(10− 26.10 ∼ 10− 28.91), respectively. Correspondingly, the free energies of forming (Δ Gfo) of these calcium arsenates were calculated to be −3787.87 kJ/mol, −3611.50 kJ/mol, −5096.47 kJ/mol and −4928.86 kJ/mol.