物理化学学报 >> 2009, Vol. 25 >> Issue (05): 953-957.doi: 10.3866/PKU.WHXB20090519

研究论文 上一篇    下一篇

高浓度V-H2O体系的溶解组分优势区域图和Pourbaix图

曾英 马旻锐   

  1. 成都理工大学材料与化学化工学院, 成都 610059
  • 收稿日期:2008-11-24 修回日期:2009-02-16 发布日期:2009-05-04
  • 通讯作者: 曾英 E-mail:zengyster@gmail.com

Predominance Diagram of Dissolved Species and Pourbaix Diagram of V-H2O Systemat High Vanadium Concentration

ZENG Ying, MA Min-Rui   

  1. College of Materials and Chemistry &Chemical Engineering, Chengdu University of Technology, Chengdu 610059, P. R. China
  • Received:2008-11-24 Revised:2009-02-16 Published:2009-05-04
  • Contact: ZENG Ying E-mail:zengyster@gmail.com

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摘要：

对25 ℃, 总V浓度cT(V)=1.0×10-3 mol·L-1时的V-H2O 体系可能存在的组分进行热力学和电化学分析, 计算了各溶解组分的浓度, 运用“浓度比较法”作为判据, 确定液相和液相、液相和固相以及各固相间的边界线, 绘制了cT(V)=1.0×10-3 mol·L-1时V-H2O 体系的溶解组分优势区域图和Pourbaix图. 与低浓度(cT(V)=1.0×10-5 mol·L-1)的优势区域图比较发现, 在一定的温度和压力下, 总钒浓度对于钒阳离子的优势区影响不大, 但对钒酸根阴离子的优势区影响显著; 随着总钒浓度的增大和酸化程度的逐步加强, 钒酸根阴离子会发生一系列复杂的质子化和聚合反应; 总钒浓度越高、酸性越强, 多核钒酸根阴离子越稳定.

关键词: V-H2O体系, 较高浓度, Pourbaix图, 优势区域图, 浓度比较法

Abstract:

The predominance diagram of dissolved species and a Pourbaix diagram of the V-H2O system with a high vanadium concentration were studied at 25 ℃ by a concentration comparison method. The concentration of dissolved species, borderlines for liquid phases or solid phases and borderlines between the solid and solid phase were calculated on the basis of thermodynamic analysis and electrochemical analysis with a total V concentration of cT(V)=1.0×10-3 mol·L-1. The predominance diagramof dissolved species and the Pourbaix diagramof the V-H2O system were then plotted. Comparisons made between predominance diagrams for cT(V)=1.0×10-3 mol·L-1 and cT(V)=1.0×10-5 mol·L-1 show that at a specific temperature and pressure the total concentration of vanadium has little effect on the stable predominance regions of the vanadium cation. These conditions also have a remarkable effect on the multi vanadium acid radical anion. A series of protonation and polymerization reactions may occur with the vanadate radical anion resulting in changes in the total concentration of vanadium and in acidity. A higher total concentration of vanadium and higher acidity result in a more stable multi-core vanadiumradical anion.

Key words: V-H2O system, Higher vanadiumconcentration, Pourbaix diagram, Predominance diagram, Concentration comparison method

MSC2000: 

  • O646