Photochemical Reactions of Benzene with Chlorine Radicals in Atmospheric Aqueous Phase

The chlorine radicals (Cl• and Cl2•−) have profound impacts on the photochemical processes in the atmospheric aqueous phase (e.g., marine clouds). However, current literature lacks information on the Cl•/Cl2•−-induced transformation of organics under sunlit irradiation. In this work, the reaction me...

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Main Authors: Linchang Dong, Yu Lei, Jun Lu, Han He, Yue Yang, Chengzhu Zhu
Format: Article
Language:English
Published: Wiley 2024-01-01
Series:Journal of Chemistry
Online Access:http://dx.doi.org/10.1155/2024/6974417
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author Linchang Dong
Yu Lei
Jun Lu
Han He
Yue Yang
Chengzhu Zhu
author_facet Linchang Dong
Yu Lei
Jun Lu
Han He
Yue Yang
Chengzhu Zhu
author_sort Linchang Dong
collection DOAJ
description The chlorine radicals (Cl• and Cl2•−) have profound impacts on the photochemical processes in the atmospheric aqueous phase (e.g., marine clouds). However, current literature lacks information on the Cl•/Cl2•−-induced transformation of organics under sunlit irradiation. In this work, the reaction mechanism of chlorine radicals with benzene (a representative VOC) in the atmospheric aqueous phase was investigated by using 355 nm laser flash photolysis, 365 nm UV light steady state, and real sunlight experiment. The results showed that Cl•/Cl2•−-initiated reactions were crucial steps for the consumption and transformation of C6H6, where the conversion rate of benzene decreases with the increase of pH and initial species concentration. Cl• attacked benzene ring to produce the Cl-CHD (6-chlorocyclohexadienyl radical) with a second-order rate constant of (1.2 ± 0.3) × 1010 M−1·s−1, while the rate constant for Cl2•− was much lower ((4.5 ± 0.3) × 106 M−1·s−1). The addition of Cl• and Cl2•− to benzene generated chlorobenzene and dichlorobenzene and ring-opening substances during the further oxidation reaction, which had been also demonstrated in the real sunlit experiments. This work provides fundamental kinetic and mechanistic insights into benzene’s photochemical transformation by Cl•/Cl2•−, facilitating the understanding of VOC transformation in atmospheric waters.
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institution Kabale University
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spelling doaj-art-818aa7dddd634d8aaa65a2442077febf2025-02-03T07:26:20ZengWileyJournal of Chemistry2090-90712024-01-01202410.1155/2024/6974417Photochemical Reactions of Benzene with Chlorine Radicals in Atmospheric Aqueous PhaseLinchang Dong0Yu Lei1Jun Lu2Han He3Yue Yang4Chengzhu Zhu5School of Resource and Environmental EngineeringKey Laboratory of PhotochemistryCentre of Analysis and MeasurementSchool of Resource and Environmental EngineeringSchool of Resource and Environmental EngineeringSchool of Resource and Environmental EngineeringThe chlorine radicals (Cl• and Cl2•−) have profound impacts on the photochemical processes in the atmospheric aqueous phase (e.g., marine clouds). However, current literature lacks information on the Cl•/Cl2•−-induced transformation of organics under sunlit irradiation. In this work, the reaction mechanism of chlorine radicals with benzene (a representative VOC) in the atmospheric aqueous phase was investigated by using 355 nm laser flash photolysis, 365 nm UV light steady state, and real sunlight experiment. The results showed that Cl•/Cl2•−-initiated reactions were crucial steps for the consumption and transformation of C6H6, where the conversion rate of benzene decreases with the increase of pH and initial species concentration. Cl• attacked benzene ring to produce the Cl-CHD (6-chlorocyclohexadienyl radical) with a second-order rate constant of (1.2 ± 0.3) × 1010 M−1·s−1, while the rate constant for Cl2•− was much lower ((4.5 ± 0.3) × 106 M−1·s−1). The addition of Cl• and Cl2•− to benzene generated chlorobenzene and dichlorobenzene and ring-opening substances during the further oxidation reaction, which had been also demonstrated in the real sunlit experiments. This work provides fundamental kinetic and mechanistic insights into benzene’s photochemical transformation by Cl•/Cl2•−, facilitating the understanding of VOC transformation in atmospheric waters.http://dx.doi.org/10.1155/2024/6974417
spellingShingle Linchang Dong
Yu Lei
Jun Lu
Han He
Yue Yang
Chengzhu Zhu
Photochemical Reactions of Benzene with Chlorine Radicals in Atmospheric Aqueous Phase
Journal of Chemistry
title Photochemical Reactions of Benzene with Chlorine Radicals in Atmospheric Aqueous Phase
title_full Photochemical Reactions of Benzene with Chlorine Radicals in Atmospheric Aqueous Phase
title_fullStr Photochemical Reactions of Benzene with Chlorine Radicals in Atmospheric Aqueous Phase
title_full_unstemmed Photochemical Reactions of Benzene with Chlorine Radicals in Atmospheric Aqueous Phase
title_short Photochemical Reactions of Benzene with Chlorine Radicals in Atmospheric Aqueous Phase
title_sort photochemical reactions of benzene with chlorine radicals in atmospheric aqueous phase
url http://dx.doi.org/10.1155/2024/6974417
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AT junlu photochemicalreactionsofbenzenewithchlorineradicalsinatmosphericaqueousphase
AT hanhe photochemicalreactionsofbenzenewithchlorineradicalsinatmosphericaqueousphase
AT yueyang photochemicalreactionsofbenzenewithchlorineradicalsinatmosphericaqueousphase
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