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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Kinetics and Mechanism of the Concurrent Reactions of Hexathionate with S(IV) and Thiosulfate in a Slightly Acidic Medium
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Kinetics and Mechanism of the Concurrent Reactions of Hexathionate with S(IV) and Thiosulfate in a Slightly Acidic Medium

机译：与S（iv）和硫代硫酸硫代硫酸钠在微酸性培养基中的同时反应的动力学和机制

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摘要

Reactions of hexathionate with thiosulfate and sulfite have been investigated by high-performance liquid chromatography via monitoring the concentration time series of tetrathionate, pentathionate, hexathionate, and thiosulfate simultaneously within the pH range of 4.0-5.0. In both reactions, elementary sulfur forms; more significant sulfur precipitation may be observed in the case of the hexathionate thiosulfate reaction, but slight turbidity in the other system means that elementary sulfur also appears in a detectable amount in the hexathionate sulfite reaction. Initial rate studies have revealed that the formal kinetic orders of both reactants in both systems are clearly unity but pH-dependence can only be observed in the case of the hexathionate sulfite reaction. The proposed kinetic model appears to suggest that nucleophilic attack of sulfite and thiosulfate may also occur on the beta- or gamma-sulfur of the polythionate chain and breakages of the a alpha-beta, beta-gamma, and gamma-gamma' bonds are all conceivable possibilities to drive the reactions. Consequently, the generally accepted sulfur -chain elongating effect of thiosulfate on longer polythionates is also proven to be accompanied by sulfur -chain shortening pathways, eventually leading to the formation of elementary sulfur.
机译：通过高效液相色谱通过监测4.0-5.0的pH范围内的浓度液相色谱通过高效液相色谱法监测四分离液，五羟基乙酯，六分离物和硫代硫酸盐的高效液相色谱反应。在两种反应中，基本硫形式;可以在六分硫代硫酸硫代硫酸酯反应的情况下观察到更明显的硫沉淀，但其他系统中的细微浊度意味着基本硫也以六分族​​亚硫酸盐反应中的可检测量出现。初始率研究表明，两个系统中两个反应物的正式动力学令显然是统一，但在亚硫酸律反应的情况下只能观察到pH依赖性。拟议的动力学模型似乎表明，亚硫酸酯和硫代硫酸盐的亲核侵袭也可能发生在α-β，β-γ和γ-gamma'键的β-或γ-硫的β-或γ-硫中存在可以想到的可能性推动反应。因此，通常接受的硫酸硫酸盐延长伸长作用较长的多硫酸盐也被证明伴有硫磺缩短途径，最终导致基本硫的形成。

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