Characterization, dissolution and solubility of the hydroxypyromorphite–hydroxyapatite solid solution [(PbxCa1−x)5(PO4)3OH] at 25 °C and pH 2–9

Geochemical Transactions

Research Article

Bin Huang¹  Yinian Zhu¹  Zongqiang Zhu¹  Yanhua Huang¹  Huili Liu¹  Meina Liang¹  Xin Zhao² 

[1] College of Environmental Science and Engineering, Guilin University of Technology, 541004, Guilin, People’s Republic of China;College of Light Industry and Food Engineering, Guangxi University, 530004, Nanning, People’s Republic of China;

关键词: Hydroxypyromorphite;    Calcium hydroxyapatite;    Solid solution;    Dissolution;    Lippmann diagram;   

DOI  :  10.1186/s12932-016-0034-8

 received in 2016-01-20, accepted in 2016-04-25,  发布年份 2016

来源: Springer

【 摘 要 】

BackgroundThe interaction between Ca-HAP and Pb2+ solution can result in the formation of a hydroxyapatite–hydroxypyromorphite solid solution [(PbxCa1−x)5(PO4)3(OH)], which can greatly affect the transport and distribution of toxic Pb in water, rock and soil. Therefore, it’s necessary to know the physicochemical properties of (PbxCa1−x)5(PO4)3(OH), predominantly its thermodynamic solubility and stability in aqueous solution. Nevertheless, no experiment on the dissolution and related thermodynamic data has been reported.ResultsDissolution of the hydroxypyromorphite–hydroxyapatite solid solution [(PbxCa1−x)5(PO4)3(OH)] in aqueous solution at 25 °C was experimentally studied. The aqueous concentrations were greatly affected by the Pb/(Pb + Ca) molar ratios (XPb) of the solids. For the solids with high XPb [(Pb0.89Ca0.11)5(PO4)3OH], the aqueous Pb2+ concentrations increased rapidly with time and reached a peak value after 240–720 h dissolution, and then decreased gradually and reached a stable state after 5040 h dissolution. For the solids with low XPb (0.00–0.80), the aqueous Pb2+ concentrations increased quickly with time and reached a peak value after 1–12 h dissolution, and then decreased gradually and attained a stable state after 720–2160 h dissolution.ConclusionsThe dissolution process of the solids with high XPb (0.89–1.00) was different from that of the solids with low XPb (0.00–0.80). The average Ksp values were estimated to be 10−80.77±0.20 (10−80.57–10−80.96) for hydroxypyromorphite [Pb5(PO4)3OH] and 10−58.38±0.07 (10−58.31–10−58.46) for calcium hydroxyapatite [Ca5(PO4)3OH]. The Gibbs free energies of formation (ΔGfo) were determined to be −3796.71 and −6314.63 kJ/mol, respectively. The solubility decreased with the increasing Pb/(Pb + Ca) molar ratios (XPb) of (PbxCa1‒x)5(PO4)3(OH). For the dissolution at 25 °C with an initial pH of 2.00, the experimental data plotted on the Lippmann diagram showed that the solid solution (PbxCa1−x)5(PO4)3(OH) dissolved stoichiometrically at the early stage of dissolution and moved gradually up to the Lippmann solutus curve and the saturation curve for Pb5(PO4)3OH, and then the data points moved along the Lippmann solutus curve from right to left. The Pb-rich (PbxCa1−x)5(PO4)3(OH) was in equilibrium with the Ca-rich aqueous solution.Graphical abstractLippmann diagrams for dissolution of the hydroxypyromorphite–hydroxyapatite solid solution [(PbxCa1−x)5(PO4)3OH] at 25 ˚C and an initial pH of 2.00.

【 授权许可】

CC BY   
© Zhu et al. 2016

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