Ce3+/Ce4+电对在硫酸和甲磺酸介质中电化学性能的差异

doi:10.61558/2993-074X.2105

电化学（中英文） ›› 2013, Vol. 19 ›› Issue (2): 141-145. doi: 10.61558/2993-074X.2105

Ce³⁺/Ce⁴⁺电对在硫酸和甲磺酸介质中电化学性能的差异

李照华，褚有群，马淳安^*

浙江工业大学绿色化学合成技术国家重点实验室培育基地，浙江杭州 310014

收稿日期:2012-02-14 修回日期:2012-03-21 出版日期:2013-04-28 发布日期:2012-03-30
通讯作者: 马淳安 E-mail:science@zjut.edu.cn
基金资助:
浙江省研究生教育创新基地基金项目（No. 1001）资助

A Comparative Study of Ce³⁺/Ce⁴⁺ Redox Couple on Pt Electrode in Sulfuric Acid and Methanesulfonic Acid

LI Zhao-hua, CHU You-qun, MA Chun-an^*

State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, China

Received:2012-02-14 Revised:2012-03-21 Published:2013-04-28 Online:2012-03-30
Contact: MA Chun-an E-mail:science@zjut.edu.cn

摘要/Abstract

摘要： 采用循环伏安法和线性扫描法研究了硫酸和甲磺酸介质中Ce³⁺/Ce⁴⁺在Pt旋转圆盘电极（RDE）上的电化学性能，初步探索了Ce³⁺/Ce⁴⁺的络合行为，考察了Ce³⁺反应的交换电流密度、扩散系数以及反应速率常数，比较了两种酸介质中Ce³⁺在Pt电极氧化的活化能. 结果表明，硫酸介质中以Ce⁴⁺的络合为主，其平衡电位负移；甲磺酸介质中以Ce³⁺的络合为主，其平衡电位正移. 硫酸介质中Pt电极上Ce³⁺更容易氧化为Ce⁴⁺, 硫酸铈(III)的电氧化对温度更为敏感.

关键词: 交换电流密度, 扩散系数, 反应速率常数, 阳极氧化, 活化能

Abstract: The electrochemical oxidations of Ce³⁺ to Ce⁴⁺ on Pt rotating disk electrode (RDE) in both sulfuric acid and methanesulfonic acid (MSA) solutions were studied by using cyclic voltammetry and linear sweep voltammetry. The complexing behaviors of Ce³⁺/Ce⁴⁺ were preliminarily probed and the exchange current density, diffusion coefficient, as well as reaction rate constant were obtained from Butler-Volmer equation. The activation energies of Ce³⁺ oxidation on Pt electrode in two types of acidic media, obtained from Arrhenius equation, were also compared. The results indicate that Ce³⁺ can be oxidized to Ce4+ much easier in sulfuric acid than in MSA solutions. The equilibrium potential in sulfuric acid solutions moves negatively due to the predominant complexation of Ce⁴⁺, while that in MSA solutions positively because of the predominant complexation of Ce³⁺, The larger values of activation energy for the oxidation of Ce³⁺ to Ce⁴⁺ on Pt electrode in sulfuric acid solutions suggest that the oxidation of Ce³⁺ occurs more readily and the electro-oxidation of cerous sulfate is more susceptible to temperature.

Key words: exchange current density, diffusion coefficient, rate constant, anode oxidation, activation energy

中图分类号:

O646.5

李照华, 褚有群, 马淳安. Ce³⁺/Ce⁴⁺电对在硫酸和甲磺酸介质中电化学性能的差异[J]. 电化学（中英文）, 2013, 19(2): 141-145.

LI Zhao-hua, CHU You-qun, MA Chun-an. A Comparative Study of Ce³⁺/Ce⁴⁺ Redox Couple on Pt Electrode in Sulfuric Acid and Methanesulfonic Acid[J]. Journal of Electrochemistry, 2013, 19(2): 141-145.

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https://electrochem.xmu.edu.cn/CN/Y2013/V19/I2/141

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Ce³⁺/Ce⁴⁺电对在硫酸和甲磺酸介质中电化学性能的差异

A Comparative Study of Ce³⁺/Ce⁴⁺ Redox Couple on Pt Electrode in Sulfuric Acid and Methanesulfonic Acid

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