A theoretical study of OH radical-initiated atmospheric oxidation of 1-chloronaphthalene

Cui, Yinan; Ding, Zhezheng; Sun, Yanhui; Yi, Yayi; Xu, Fei; Zhang, Qingzhu; Wang, Wenxing

doi:10.1016/j.cplett.2018.03.032

Cited by 8 publications

(2 citation statements)

References 36 publications

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“…Heterogeneous photocatalysis involves the absorption of photons by a semiconductor with an energy equal to or greater than that of the band gap (E c − E v ), facilitating the flow of electrons from the valence band (E v ) to the conduction band (E c ) [12,13]. This process generates a positive hole (h+) at the valence band and releases an electron (e−) into the conduction band [14,15].…”

Section: Introductionmentioning

confidence: 99%

Kinetic Modeling of the Photocatalytic Degradation of Chlorinated Aromatic Volatile Organic Compounds: Mass Transfer Enhancement

Koné,

Assadi,

Belkessa

et al. 2024

Applied Sciences

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Chlorobenzene (CB) and Chloronaphthalene (CN) emissions from cement plant operations pose significant environmental risks. This study investigates the mass transfer effects of chlorinated aromatic Volatile Organic Compounds (VOCs), specifically CB and CN, in the gas phase of a continuous-tangential-flow annular photocatalytic reactor. The experiments involved introducing CB and CN into the reactor, and the degradation kinetics were analyzed using the Langmuir–Hinshelwood (L-H) model. The L-H model was applied to assess the impact of the flow rate, concentration, and relative humidity (% RH) on the degradation rate (DR). The results indicate that both the experimental and simulated degradation rates improved with increased flow rates (1 to 9 m3·h−¹) and inlet concentrations (30 to 216 mg·m−3). This enhancement of the DR correlates with the availability of active OH* species on the TiO2 surface. The L-H model emphasizes the role of H2O molecules in VOC removal kinetics. The degradation rates increased with a rising water content (5 to 55%), but adverse effects on VOC conversion were observed beyond a 55% RH. This study reveals a mass transfer effect, with internal diffusional limitations in the TiO2 pores under operational conditions. The kinetics were predominantly controlled by chemical kinetics and catalyst pore availability. Furthermore, this study demonstrates a higher CB degradation than CN in the reactor and experimental conditions. For a concentration of 1.328 mM·m−3, the CB DR ranged from 0.70 to 2.84 µM·m2·s−¹, as the flow rate varied from 1 to 9 m3·h−¹. The CN DR varied from 0.60 to 2.20 µM·m2·s−¹ within the same flow rate range.

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Section: Introductionmentioning

confidence: 99%

Kinetic Modeling of the Photocatalytic Degradation of Chlorinated Aromatic Volatile Organic Compounds: Mass Transfer Enhancement

Koné,

Assadi,

Belkessa

et al. 2024

Applied Sciences

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“…It is known that quantum chemistry is an effective method to understand the mechanism of chemical reaction by calculating the charge distribution, molecular properties, and potential energy surfaces of reactions. Many studies have shown that density functional theory (DFT) is a powerful tool to calculate the reaction pathways, kinetics, and byproducts of target compounds under specific ambient conditions. , According to DFT calculations, • OH and • Cl initial reactions were via • OH ( • Cl) addition to unsaturated bonds or H-abstraction with target compounds in the atmosphere or an aquatic environment. − Thus, the reaction mechanism of reactive species with target compounds in the UV/chlorine process can be further investigated using DFT calculations.…”

Section: Introductionmentioning

confidence: 99%

Kinetics and Mechanism of Degradation of Reactive Radical-Mediated Probe Compounds by the UV/Chlorine Process: Theoretical Calculation and Experimental Verification

Peng

Lei

et al. 2022

ACS Omega

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The UV/chlorine process, by combining chlorination with UV irradiation, has been recently considered as a highly efficient advanced oxidation process (AOP) technology in water treatment. Nitrobenzene (NB), benzoic acid (BA), and p-chlorobenzoic acid (pCBA) are widely used as model probe compounds in the UV/chlorine system to calculate the second-order rate constants of the specific radical reaction with target contaminates by a competitive kinetics method. A comprehensive understanding of probe compounds' reaction mechanism with reactive radicals is critical for investigation of the UV/chlorine reaction system. Here, we evaluated the radical-mediated reaction kinetics and mechanism of NB, BA, and pCBA in the UV/chlorine process using theoretical calculations and experimental studies. The main reactive radicals • OH, • ClO, and • Cl in the UV/chlorine process for the initial reaction with NB, BA, and pCBA can be explained by H-abstraction and addition pathways. The ΔE 0,≠ values for the • OH reaction with NB, BA, and pCBA were in the range of 5.0−8.0, 3.7−8.2, and 3.4−8.2 kcal mol −1 , respectively. The ΔE 0,≠ values for • ClO and • Cl reactions with these three probe compounds were higher than those of • OH, indicating slower • ClO-and • Cl-initiated reactions than that of the • OH-initiated reaction. The theoretically calculated radical-mediated reaction kinetic rate constants (k CP C ) for NB, BA, and pCBA were 4.58 × 10 −3 , 1.28 × 10 −2 , and 1.6 × 10 −2 s −1 , respectively, which was consistent with the experimentally determined pseudo-first-order rate constant (k CP RR ) in the UV/chlorine process. Interestingly, theoretical calculations showed that • ClO and • Cl played an important role in subsequent reactions of NB-OH radicals, converting to hydroxylated and chlorinated products, which were further confirmed by experimental products' identification. The findings from this study indicated that quantum chemistry calculations provide an effective means to investigate the reaction kinetics and mechanism of chemicals in the UV/chlorine process.

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The formation mechanism of highly oxygenated organic molecules produced by toluene in the urban atmosphere

Dong

Tang

Liu

et al. 2023

Atmospheric Environment

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A theoretical study of OH radical-initiated atmospheric oxidation of 1-chloronaphthalene

Cited by 8 publications

References 36 publications

Kinetic Modeling of the Photocatalytic Degradation of Chlorinated Aromatic Volatile Organic Compounds: Mass Transfer Enhancement

Kinetic Modeling of the Photocatalytic Degradation of Chlorinated Aromatic Volatile Organic Compounds: Mass Transfer Enhancement

Kinetics and Mechanism of Degradation of Reactive Radical-Mediated Probe Compounds by the UV/Chlorine Process: Theoretical Calculation and Experimental Verification

The formation mechanism of highly oxygenated organic molecules produced by toluene in the urban atmosphere

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