Highly efficient photoinitiation in the cerium(III)-catalyzed aqueous autoxidation of sulfur(IV). An example of comprehensive evaluation of photoinduced chain reactions

Ildikó Kerezsi, G. Lente, I. Fábián

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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.

Original languageEnglish
Pages (from-to)4785-4793
Number of pages9
JournalJournal of the American Chemical Society
Volume127
Issue number13
DOIs
Publication statusPublished - Apr 6 2005

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Cerium
Sulfur
Sulfites
Ions
Oxygen
Light
Spectrophotometers
Lighting
Sulfates
Diodes
Iron
Oxidation
Catalysts
Chemical analysis

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Highly efficient photoinitiation in the cerium(III)-catalyzed aqueous autoxidation of sulfur(IV). An example of comprehensive evaluation of photoinduced chain reactions",
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.",
author = "Ildik{\'o} Kerezsi and G. Lente and I. F{\'a}bi{\'a}n",
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AU - Kerezsi, Ildikó

AU - Lente, G.

AU - Fábián, I.

PY - 2005/4/6

Y1 - 2005/4/6

N2 - 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.

AB - 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.

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