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An Experimental and Master Equation Investigation of Kinetics of the CH₂OO + RCN Reactions (R = H, CH₃, C₂H₅) and Their Atmospheric Relevance.

ABSTRACT: We have performed direct kinetic measurements of the CH₂OO + RCN reactions (R = H, CH₃, C₂H₅) in the temperature range 233-360 K and pressure range 10-250 Torr using time-resolved UV-absorption spectroscopy. We have utilized a new photolytic precursor, chloroiodomethane (CH₂ICl), whose photolysis at 193 nm in the presence of O₂ produces CH₂OO. Observed bimolecular rate coefficients for CH₂OO + HCN, CH₂OO + CH₃CN, and CH₂OO + C₂H₅CN reactions at 296 K are (2.22 ± 0.65) × 10^-14 cm³ molecule^-1 s^-1, (1.02 ± 0.10) × 10^-14 cm³ molecule^-1 s^-1, and (2.55 ± 0.13) × 10^-14 cm³ molecule^-1 s^-1, respectively, suggesting that reaction with CH₂OO is a potential atmospheric degradation pathway for nitriles. All the reactions have negligible temperature and pressure dependence in the studied regions. Quantum chemical calculations (ωB97X-D/aug-cc-pVTZ optimization with CCSD(T)-F12a/VDZ-F12 electronic energy correction) of the CH₂OO + RCN reactions indicate that the barrierless lowest-energy reaction path leads to a ring closure, resulting in the formation of a 1,2,4-dioxazole compound. Master equation modeling results suggest that following the ring closure, chemical activation in the case of CH₂OO + HCN and CH₂OO + CH₃CN reactions leads to a rapid decomposition of 1,2,4-dioxazole into a CH₂O + RNCO pair, or by a rearrangement, into a formyl amide (RC(O)NHC(O)H), followed by decomposition into CO and an imidic acid (RC(NH)OH). The 1,2,4-dioxazole, the CH₂O + RNCO pair, and the CO + RC(NH)OH pair are atmospherically significant end products to varying degrees.

SUBMITTER: Franzon L

PROVIDER: S-EPMC9869398 | biostudies-literature | 2023 Jan

REPOSITORIES: biostudies-literature

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An Experimental and Master Equation Investigation of Kinetics of the CH2OO + RCN Reactions (R = H, CH3, C2H5) and Their Atmospheric Relevance.

Franzon Lauri L Peltola Jari J Valiev Rashid R Vuorio Niko N Kurtén Theo T Eskola Arkke A

The journal of physical chemistry. A 20230101 2

We have performed direct kinetic measurements of the CH2OO + RCN reactions (R = H, CH3, C2H5) in the temperature range 233-360 K and pressure range 10-250 Torr using time-resolved UV-absorption spectroscopy. We have utilized a new photolytic precursor, chloroiodomethane (CH2ICl), whose photolysis at 193 nm in the presence of O2 produces CH2OO. Observed bimolecular rate coefficients for CH2OO + HCN, CH2</ ...[more]

PMID: 36602183

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Project description:The fluorescence assay by gas expansion (FAGE) method for the measurement of the methyl peroxy radical (CH3O2) using the conversion of CH3O2 into methoxy radicals (CH3O) by excess NO, followed by the detection of CH3O, has been used to study the kinetics of the self-reaction of CH3O2. Fourier transform infrared (FTIR) spectroscopy has been employed to determine the products methanol and formaldehyde of the self-reaction. The kinetics and product studies were performed in the Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC) in the temperature range 268-344 K at 1000 mbar of air. The product measurements were used to determine the branching ratio of the reaction channel forming methoxy radicals, rCH3O. A value of 0.34 ± 0.05 (errors at 2σ level) was determined for rCH3O at 295 K. The temperature dependence of rCH3O can be parametrized as rCH3O = 1/{1 + [exp(600 ± 85)/T]/(3.9 ± 1.1)}. An overall rate coefficient of the self-reaction of (2.0 ± 0.9) × 10-13 cm3 molecule-1 s-1 at 295 K was obtained by the kinetic analysis of the observed second-order decays of CH3O2. The temperature dependence of the overall rate coefficient can be characterized by koverall = (9.1 ± 5.3) × 10-14 × exp((252 ± 174)/T) cm3 molecule-1 s-1. The found values of koverall in the range 268-344 K are ∼40% lower than the values calculated using the recommendations of the Jet Propulsion Laboratory and IUPAC, which are based on the previous studies, all of them utilizing time-resolved UV-absorption spectroscopy to monitor CH3O2. A modeling study using a complex chemical mechanism to describe the reaction system showed that unaccounted secondary chemistry involving Cl species increased the values of koverall in the previous studies using flash photolysis to initiate the chemistry. The overestimation of the koverall values by the kinetic studies using molecular modulation to generate CH3O2 can be rationalized by a combination of underestimated optical absorbance of CH3O2 and unaccounted CH3O2 losses to the walls of the reaction cells employed.

Dataset Information

An Experimental and Master Equation Investigation of Kinetics of the CH₂OO + RCN Reactions (R = H, CH₃, C₂H₅) and Their Atmospheric Relevance.

Publications

An Experimental and Master Equation Investigation of Kinetics of the CH<sub>2</sub>OO + RCN Reactions (R = H, CH<sub>3</sub>, C<sub>2</sub>H<sub>5</sub>) and Their Atmospheric Relevance.

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