The reactions of chlorine dioxide with inorganic and organic compounds in water treatment: kinetics and mechanisms,Environmental Science: Water Research & Technology

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The reactions of chlorine dioxide with inorganic and organic compounds in water treatment: kinetics and mechanisms
Environmental Science: Water Research & Technology ( IF 3.5 ) Pub Date : 2020-07-15 , DOI: 10.1039/d0ew00231c
Wenhui Gan _{1,

2,

3,

4,

5} , Yuexian Ge _{1,

2,

3,

4,

5} , Yu Zhong _{1,

2,

3,

4,

5} , Xin Yang _{1,

2,

3,

4,

5}

Affiliation

Chlorine dioxide (ClO₂), as an alternative to chlorine, has been widely applied in water treatment. In order to better understand the performance of ClO₂ in water treatment, the kinetics and mechanisms of ClO₂ reactions with inorganic and organic compounds found in waters are critically reviewed. In the case of inorganic compounds, ClO₂ reacts with I⁻, CN⁻, NO₂⁻, SO₃²⁻, Fe(II) and Mn(II) rapidly at apparent second-order reaction rate constants (k_app) of 10²–10⁶ M⁻¹ s⁻¹ at pH 7.0 and barely reacts with NH₄⁺ and Br⁻. In the case of organic compounds, ClO₂ selectively reacts with compounds with electron-rich moieties, such as phenols (k_app = 10³–10⁹ M⁻¹ s⁻¹), anilines (k_app = 10⁵–10⁸ M⁻¹ s⁻¹), and thiols (k_app > 10⁸ M⁻¹ s⁻¹). ClO₂ also shows high reactivity towards aliphatic tertiary amines and heterocyclic nitrogenous compounds (i.e., indoles and piperidines) with k_app of 10¹–10⁶ M⁻¹ s⁻¹ at pH 7.0, but low reactivity with unsaturated structures (i.e., olefins and aldehydes). The k_app values at pH 7.0 in ClO₂ oxidation vary over 14 orders of magnitude. Electron transfer is the dominant pathway for ClO₂ reactions. Quantitative structure–activity relationships (QSARs) can be used to predict the species-specific secondary reaction rate constants for ClO₂ oxidation of compounds containing phenolic and amine structures. Little modifications are expected on the structure of the parent compounds upon the primary attack of ClO₂, but further oxidation generally leads to the formation of quinones, aldehydes and carboxylic acids. Furthermore, the transformation kinetics of inorganic compounds, typical organic compounds and emerging micropollutants are compared and their half-life times under typical water treatment conditions during ClO₂ oxidation are calculated.

中文翻译：

水处理中二氧化氯与无机和有机化合物的反应：动力学和机理

作为二氯的替代物，二氧化氯（ClO ₂）已广泛应用于水处理中。为了更好地理解CLO的性能₂水处理，CLO的动力学和机制₂反应与无机和有机化合物在水中发现的严格审查。在无机化合物的情况下，CLO _2种发生反应与I ^-，CN ^-，NO ₂^-，SO ₃^2-，Fe（上II）和Mn（II）迅速在表观二级反应速率常数（ķ_应用程式的）10 ² –10 ⁶ M^-1小号^-1，pH为7.0和勉强NH反应₄⁺和Br^-。对于有机化合物，ClO₂与具有高电子部分的化合物（例如苯酚（ k _app = 10³ –10⁹ M^-1 s^-1），苯胺（ k _app = 10⁵ –10⁸ M）选择性地反应^-1 s^-1）和硫醇（ k _app > 10⁸ M^-1 s^-1）。CLO₂还示出了对脂族叔胺和杂环含氮化合物（高反应性，即用，吲哚类和哌啶）ķ_应用程式10 ¹ -10 ⁶中号^-1小号^-1，pH为7.0，但反应性低与不饱和结构（即，烯烃和醛）。所述ķ_应用在CLO在pH 7.0的值₂氧化变化超过14个数量级。电子转移是ClO ₂反应的主要途径。定量构效关系（QSAR）可用于预测ClO ₂的物种特异性二级反应速率常数氧化含有酚和胺结构的化合物。在ClO ₂的初次攻击下，预期对母体化合物的结构几乎没有修饰，但是进一步的氧化通常导致醌，醛和羧酸的形成。此外，比较了无机化合物，典型的有机化合物和新兴的微污染物的转化动力学，并计算了它们在ClO ₂氧化过程中典型水处理条件下的半衰期。

更新日期：2020-08-27

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