在含氧水溶液中四氯化碳的单电子还原：由三氯过氧化自由基介导的氯离子和二氧化碳的形成。
One electron reduction of CCl4 in oxygenated aqueous solutions: a CCl3O2-free radical mediated formation of Cl- and CO2.
作者信息
Mönig J, Bahnemann D, Asmus K D
出版信息
Chem Biol Interact. 1983 Oct 15;47(1):15-27. doi: 10.1016/0009-2797(83)90144-8.
Product yields have been determined after one-electron-induced reduction of CCl4 in aqueous solutions containing t-butanol and various concentrations of oxygen. It was shown that CCl3 radicals add oxygen to form CCl3O2 radicals, which eventually yield three chloride ions and CO2. A constant ratio of G(Cl-)/G(CO2) = 4 is found in solutions containing 1.5 X 10(-4) M or more oxygen. Competing reactions of the CCl3 radical increase this ratio at lower oxygen concentrations. The rate constant for the oxygen addition to CCl3 radicals was determined by pulse radiolysis to 3.3 X 10(9) M-1 s-1. Possible reaction mechanisms leading to the observed end products are discussed.
在含有叔丁醇和不同浓度氧气的水溶液中，通过单电子诱导还原四氯化碳后测定了产物产率。结果表明，三氯自由基与氧气加成形成三氯过氧化自由基，最终生成三个氯离子和二氧化碳。在含有1.5×10⁻⁴M或更高浓度氧气的溶液中，发现G(Cl⁻)/G(CO₂)的恒定比值为4。在较低氧气浓度下，三氯自由基的竞争反应会使该比值增加。通过脉冲辐解测定了氧气与三氯自由基加成的速率常数为3.3×10⁹M⁻¹s⁻¹。讨论了导致观察到的最终产物的可能反应机理。
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