水氧化还原反应中电极电势的计算和讨论
计算电极电势是电化学的必备技能。目前物理化学教材中,一般只给出了酸性条件下部分物质的标准电极电势(φӨ),以及如何利用Nernst方程由φӨ计算电极电势(φ)。教材中对于碱性条件下φBӨ没有涉及,学生对φBӨ不甚理解,乃至在由φBӨ计算φ时可能得到错误的结果和结论。本文以水(H2O)氧化还原反应为例,从物质的标准生成Gibbs自由能变(△fGmӨ)出发计算φӨ和φBӨ,结合酸(或碱)性条件下反应物种的分析,利用Nernst方程计算不同p H下的φ,给出φ-p H图。此外,还讨论了热力学同位素效应对φӨ和φ的影响。这可为作为相关教学和科研的参考。...
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| Published in | 大学化学 Vol. 39; no. 8; pp. 351 - 358 |
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| Main Authors | , , , |
| Format | Journal Article |
| Language | Chinese |
| Published |
北京大学
28.08.2024
中国化学会 西北大学化学与材料科学学院,西安 710127 |
| Subjects | |
| Online Access | Get full text |
| ISSN | 1000-8438 |
| DOI | 10.3866/PKU.DXHX202401031 |
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| Abstract | 计算电极电势是电化学的必备技能。目前物理化学教材中,一般只给出了酸性条件下部分物质的标准电极电势(φӨ),以及如何利用Nernst方程由φӨ计算电极电势(φ)。教材中对于碱性条件下φBӨ没有涉及,学生对φBӨ不甚理解,乃至在由φBӨ计算φ时可能得到错误的结果和结论。本文以水(H2O)氧化还原反应为例,从物质的标准生成Gibbs自由能变(△fGmӨ)出发计算φӨ和φBӨ,结合酸(或碱)性条件下反应物种的分析,利用Nernst方程计算不同p H下的φ,给出φ-p H图。此外,还讨论了热力学同位素效应对φӨ和φ的影响。这可为作为相关教学和科研的参考。 |
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| AbstractList | G64%O6; 计算电极电势是电化学的必备技能.目前物理化学教材中,一般只给出了酸性条件下部分物质的标准电极电势(φθ),以及如何利用Nernst方程由φθ计算电极电势(φ).教材中对于碱性条件下φBθ没有涉及,学生对φBθ不甚理解,乃至在由φBθ计算φ时可能得到错误的结果和结论.本文以水(H2O)氧化还原反应为例,从物质的标准生成Gibbs自由能变(?fGmθ)出发计算φθ和φBθ,结合酸(或碱)性条件下反应物种的分析,利用Nernst方程计算不同pH下的φ,给出φ-pH图.此外,还讨论了热力学同位素效应对φθ和φ的影响.这可为作为相关教学和科研的参考. 计算电极电势是电化学的必备技能。目前物理化学教材中,一般只给出了酸性条件下部分物质的标准电极电势(φӨ),以及如何利用Nernst方程由φӨ计算电极电势(φ)。教材中对于碱性条件下φBӨ没有涉及,学生对φBӨ不甚理解,乃至在由φBӨ计算φ时可能得到错误的结果和结论。本文以水(H2O)氧化还原反应为例,从物质的标准生成Gibbs自由能变(△fGmӨ)出发计算φӨ和φBӨ,结合酸(或碱)性条件下反应物种的分析,利用Nernst方程计算不同p H下的φ,给出φ-p H图。此外,还讨论了热力学同位素效应对φӨ和φ的影响。这可为作为相关教学和科研的参考。 |
| Abstract_FL | In electrochemistry,φ can be calculated via φθ and Nernst equation.Current physical chemistry textbooks only provide substances'φθ under acidic conditions and corresponding practices.Hence,the calculation of φ works well under acidic conditions.However,it becomes complicated under alkaline conditions for some substances cannot exist in acidic conditions.These might lead to incorrect results and confused conclusions.To address this issue,the present study calculates φθ(φBθ) from ?rGmθ based on ?fGmθ of involved substances in redox half reaction.Then,φ at different pH is calculated via Nernst equation,resulting in a φ-pH diagram.Moreover,thermodynamic isotope effects on φθ and φ are included.This may serve as a reference for teaching and research purposes. |
| Author | 郭慧林 刘季铨 杨鹰 郭晓辉 |
| AuthorAffiliation | 西北大学化学与材料科学学院,西安 710127 |
| AuthorAffiliation_xml | – name: 西北大学化学与材料科学学院,西安 710127 |
| Author_FL | Ji-Quan Liu Huilin Guo Ying Yang Xiaohui Guo |
| Author_FL_xml | – sequence: 1 fullname: Ji-Quan Liu – sequence: 2 fullname: Huilin Guo – sequence: 3 fullname: Ying Yang – sequence: 4 fullname: Xiaohui Guo |
| Author_xml | – sequence: 1 fullname: 刘季铨 organization: 西北大学化学与材料科学学院,西安710127 – sequence: 2 fullname: 郭慧林 organization: 西北大学化学与材料科学学院,西安710127 – sequence: 3 fullname: 杨鹰 organization: 西北大学化学与材料科学学院,西安710127 – sequence: 4 fullname: 郭晓辉 organization: 西北大学化学与材料科学学院,西安710127 |
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| DocumentTitle_FL | Calculation and Discussion of Electrode Potentials in Redox Reactions of Water |
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| Keywords | 水氧化还原反应 电极电势计算 φ-pH图 热力学同位素效应 Redox reactions of water Electrode potential calculation φ-pH Diagram Thermodynamic isotope effect |
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| Title | 水氧化还原反应中电极电势的计算和讨论 |
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