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• W2014201382 abstract "The photoinitiated and cerium(III)-catalyzed aqueous reaction between sulfite ion and oxygen has been studied in a diode-array spectrophotometer using the same light beam for excitation and detection. Cerium(III) is identified as the photoactive absorbing species, and the production of cerium(IV) initiates a radical chain reaction. To interpret all the experimental findings, a simple scheme is proposed, in which the additional chain carriers are sulfite ion radical (SO3-•), sulfate ion radical (SO4-•), and peroxomonosulfate ion radical (SO5-•). The overall rate of oxidation is proportional to the square root of the light intensity per unit volume, which is readily interpreted by the second-order termination reaction of the proposed scheme. It is also shown that the reaction proceeds for an extended period of time in the dark following illumination, and a quantitative analysis is presented for this phase as well. The postulated model predicts that cerium(III) should have a cocatalytic or synergistic effect on the autoxidation of sulfite ion in the presence of other catalysts. This prediction was confirmed in the iron(III)−sulfite ion−oxygen system. The experimental method and the mathematical treatment used might be applicable to a wide range of photoinduced chain reactions." @default.
• W2014201382 created "2016-06-24" @default.
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• W2014201382 date "2005-03-10" @default.
• W2014201382 modified "2023-10-18" @default.
• W2014201382 title "Highly Efficient Photoinitiation in the Cerium(III)-Catalyzed Aqueous Autoxidation of Sulfur(IV). An Example of Comprehensive Evaluation of Photoinduced Chain Reacions" @default.
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• W2014201382 doi "https://doi.org/10.1021/ja0439120" @default.
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