氧自由基相互转化反应的能量学

W.H. Koppenol, J. Butler
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引用次数: 241

摘要

综述了含氧自由基反应的能量学。首先介绍了含氧自由基和含氢自由基的热力学数据,其次是金属配合物和金属蛋白、含卤素自由基和有机自由基的热力学数据。我们的方法是借助还原势计算吉布能变化。如果一个特定的势是未知的,我们用热力学循环的方法来估计它。假设和估计的数量随着所涵盖主题的顺序而增加。因此,我们对含氢和含氧物质的反应的计算是相当严谨的,而与有机自由基有关的结论则比较试探性。特别讨论了过氧化氢、低氧化态金属离子、对苯二酚、次卤化物离子和抗坏血酸等导致超氧自由基、羟基自由基和单线态氧等短寿命物质的反应。附录包含关于电极电位和氧在水中溶解度数据的约定。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Energetics of interconversion reactions of oxyradicals

The energetics of reactions involving oxyradicals are reviewed. Thermodynamic data of radical species containing O and H are presented first, followed by those of metallocomplexes and metalloproteins, halogen containing species and organic radicals. Our approach is to calculate Gibb energy changes with the help of reduction potentials. If a particular potential is unknown, we estimate it by way of a thermodynamic cycle. The number of assumptions and estimates increases with the order of the topics covered. Thus, our calculations regarding reactions involving H and O containing species are quite rigorous, while conclusions related to organic radicals are more tentative. In particular reactions of hydrogen peroxide, metal ions in lower oxidation states, hydroquinones, hypohalide ions and ascorbic acid leading to short-lived species such as superoxide radical, hydroxyl radical and singlet oxygen are discussed. Appendices contain conventions regarding electrode potentials and solubility data of oxygen in water.

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