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›› 2012, Vol. 12 ›› Issue (5): 857-863.

• 材料工程专栏 • 上一篇    下一篇

Ti-O体系化合物的生成吉布斯自由能的计算与分析

杨帆 李钒 姚传好 于志辉 夏定国   

  1. 北京工业大学环境与能源工程学院 北京工业大学环境与能源工程学院 北京工业大学环境与能源工程学院 北京工业大学环境与能源工程学院 北京大学工学院
  • 收稿日期:2012-08-06 修回日期:2012-10-08 出版日期:2012-10-20 发布日期:2012-10-20
  • 通讯作者: 李钒

Calculation and Analysis of the Standard Gibbs Free Energy of Formation for Ti-O Compounds

YANG Fan LI Fan YAO Chuan-hao YU Zhi-hui XIA Ding-guo   

  1. College of Environmental and Energy Engineering, Beijing University of Technology College of Environmental and Energy Engineering, Beijing University of Technology College of Environmental and Energy Engineering, Beijing University of Technology College of Environmental and Energy Engineering, Beijing University of Technology College of Engineering, Peking University
  • Received:2012-08-06 Revised:2012-10-08 Online:2012-10-20 Published:2012-10-20
  • Contact: LI Fan

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摘要： 应用氧势递增原理对Ti-O体系中24种化合物的标准生成吉布斯自由能DfG0进行了计算分析. 结果显示，1304 K时Ti26O51与Ti28O55平衡的氧势和Ti24O47与Ti26O51平衡的氧势违背了氧势递增原理，表明Ti24O47, Ti26O51和Ti28O55三种物质的DfG0数据中至少一个有误. 在详细介绍用氧势递增原理和拟抛物线规则估算DfG0方法的基础上，分别对这3种氧化物的DfG0进行了估算，两种方法的计算结果一致，1304 K时DfG0Ti24O47=-16785.366±0.011 kJ/mol, DfG0Ti26O51= -18202.261±0.021 kJ/mol, DfG0Ti284O55=-19619.080±0.008 kJ/mol. 对估算结果分析认为，原Ti26O51的DfG0有误的可能性最大. 依据评估后的数据，以碳热还原和氢气还原TiO2制备了Ti4O7.

关键词: Ti-O化合物, 标准生成吉布斯自由能, 氧势递增原理, 拟抛物线规则

Abstract: The rule of oxygen potential increasing with oxygen mole fraction in oxides and calculation with computer are applied to assess the data of standard Gibbs free energy of formation DfG0 for 24 types of Ti-O compounds obtained from literatures. The results show that the relationship of oxygen potential with the equilibrium reactions of Ti26O51 with Ti28O55 and Ti24O47 with Ti26O51 do not obey the rule of oxygen potential increasing at 1304 K. It is suspected that one of DfG0 data of Ti24O47, Ti26O51, and Ti28O55 is error. The methods of evaluating DfG0 by both the oxygen potential increasing and quasi-parabola rules are explained in detail. Then DfG0 data of Ti24O47, Ti26O51, and Ti28O55 are separately evaluated. The results obtained by the two different methods are the same. At 1304 K they are DfG0Ti24O47=-16785.366±0.011 kJ/mol, DfG0Ti26O51=-18202.261±0.021 kJ/mol, DfG0Ti28O55=-19619.080±0.008 kJ/mol. These results are analyzed, which shows that the original value in DfG0 of Ti26O51 is probably larger error. Based on the assessed data, Ti4O7 material is prepared from TiO2 by carbothermal and hydrogen reduction methods.

Key words: Ti-O compound, standard Gibbs free energy, oxygen potential increasing rule, quasi-parabola rule

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