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Accurate Kinetic Studies of OH + HO₂ Radical-Radical Reaction through Direct Measurement of Precursor and Radical Concentrations with High-Resolution Time-Resolved Dual-Comb Spectroscopy.

ABSTRACT: The radical-radical reaction between OH and HO₂ has been considered for a long time as an important reaction in tropospheric photochemistry and combustion chemistry. However, a significant discrepancy of an order of magnitude for rate coefficients of this reaction is found between two recent experiments. Herein, we investigate the reaction OH + HO₂ via direct spectral quantification of both the precursor (H₂O₂) and free radicals (OH and HO₂) upon the 248 nm photolysis of H₂O₂ using infrared two-color time-resolved dual-comb spectroscopy. With quantitative and kinetic analysis of concentration profiles of both OH and HO₂ at varied conditions, the rate coefficient k_OH+HO₂ is determined to be (1.10 ± 0.12) × 10^-10 cm³ molecule^-1 s^-1 at 296 K. Moreover, we explore the kinetics of this reaction under conditions in the presence of water, but no enhancement in the k_OH+HO₂ can be observed. This work as an independent experiment plays a crucial role in revisiting this prototypical radical-radical reaction.

SUBMITTER: Chen IY

PROVIDER: S-EPMC11017308 | biostudies-literature | 2024 Apr

REPOSITORIES: biostudies-literature

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Accurate Kinetic Studies of OH + HO2 Radical-Radical Reaction through Direct Measurement of Precursor and Radical Concentrations with High-Resolution Time-Resolved Dual-Comb Spectroscopy.

Chen I-Yun IY Chang Che-Wei CW Fittschen Christa C Luo Pei-Ling PL

The journal of physical chemistry letters 20240328 14

The radical-radical reaction between OH and HO2 has been considered for a long time as an important reaction in tropospheric photochemistry and combustion chemistry. However, a significant discrepancy of an order of magnitude for rate coefficients of this reaction is found between two recent experiments. Herein, we investigate the reaction OH + HO2 via direct spectral quantification of both the precursor (H2O2) and free radicals (OH and HO2) ...[more]

PMID: 38547368

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Project description:We investigated the reactions of the hydroxyl radical (OH) with cyclopentenone derivatives and cyclopentanone in a quasi-static reaction cell at 4 Torr across a 300-500 K temperature range. The OH radicals were generated using pulsed laser photolysis of hydrogen peroxide vapors, and the ketone reactants were introduced in excess. The relative concentrations of the radicals were monitored as a function of reaction time using laser-induced fluorescence. At room temperature, the reaction rate coefficients were measured to be 1.2(±0.1) × 10-11 cm3 s-1 for reaction with 2-cyclopenten-1-one (R1); 1.7(±0.2) × 10-11 cm3 s-1 for reaction with 2-methyl-2-cyclopenten-1-one (R2); and 4.4(±0. 7) × 10-12 cm3 s-1 for reaction with 3-methyl-2-cyclopenten-1-one (R3). Over the experimental temperature range, the rate coefficients can be fitted with the modified Arrhenius expressions k1(T) = 1.2 × 10-11 (T/300)0.26 exp (6.7 kJ mol-1/R {1/T - 1/300}) cm3 s-1, k2(T) = 1.7 × 10-11 (T/300)6.4 exp (27.6 kJ mol-1/R {1/T - 1/300}) cm3 s-1, k3(T) = 4.4 × 10-12 (T/300)17.8 exp (57.8 kJ mol-1/R {1/T - 1/300}) cm3 s-1. In the cases of 2-cyclopenten-1-one and 2-methyl-2-cyclopenten-1-one, the temperature dependence of the rate coefficients is similar to that calculated or measured for noncyclic conjugated ketones. We also found that the reaction with 3-methyl-2-cyclopenten-1-one was slower, with rate coefficients similar to those measured for the reaction with the saturated cyclic ketone cyclopentanone. To discuss the experimental data, we use potential energy surfaces (PES) calculated at the CCSD(T)/cc-pVTZ//M06-2X/6-311+G** level of theory. RRKM-based Master equation calculations were also performed to infer the most likely reaction products over a wide range of temperatures and pressures. We suggest that both abstraction and addition mechanisms contribute to the overall OH removal, forming radical products stabilized by resonance. We also discuss the relevance for combustion and atmospheric chemistry.

Dataset Information

Accurate Kinetic Studies of OH + HO₂ Radical-Radical Reaction through Direct Measurement of Precursor and Radical Concentrations with High-Resolution Time-Resolved Dual-Comb Spectroscopy.

Publications

Accurate Kinetic Studies of OH + HO<sub>2</sub> Radical-Radical Reaction through Direct Measurement of Precursor and Radical Concentrations with High-Resolution Time-Resolved Dual-Comb Spectroscopy.

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