An experimental and master-equation modeling study of the kinetics of the reaction between resonance-stabilized (CH3)2CCHCH2 radical and molecular oxygen

文献情報

出版日 2021-08-02
DOI 10.1039/D1CP02210E
インパクトファクター 3.676
著者

Satya P. Joshi, Timo T. Pekkanen, Prasenjit Seal, Raimo S. Timonen, Arkke J. Eskola


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要旨

The kinetics of the reaction between resonance-stabilized (CH3)2CCHCH2 radical (R) and O2 has been investigated using photoionization mass spectrometry, and master equation (ME) simulations were performed to support the experimental results. The kinetic measurements of the (CH3)2CCHCH2 + O2 reaction (1) were carried out at low helium bath-gas pressures (0.2–5.7 Torr) and over a wide temperature range (238–660 K). Under low temperature (238–298 K) conditions, the pressure-dependent bimolecular association reaction R + O2 → ROO determines kinetics, until at an intermediate temperature range (325–373 K) the ROO adduct becomes thermally unstable and increasingly dissociates back to the reactants with increasing temperature. The initial association of O2 with (CH3)2CCHCH2 radical occurs on two distinct sites: terminal 1(t) and non-terminal 1(nt) sites on R, leading to the barrierless formation of ROO(t) and ROO(nt) adducts, respectively. Important for autoignition modelling of olefinic compounds, bimolecular reaction channels appear to open for the R + O2 reaction at high temperatures (T > 500 K) and pressure-independent bimolecular rate coefficients of reaction (1) with a weak positive temperature dependence, (2.8–4.6) × 10−15 cm3 molecule−1 s−1, were measured in the temperature range of 500–660 K. At a temperature of 501 K, a product signal of reaction (1) was observed at m/z = 68, probably originating from isoprene. To explore the reaction mechanism of reaction (1), quantum chemical calculations and ME simulations were performed. According to the ME simulations, without any adjustment to energies, the most important and second most important product channels at the high temperatures are isoprene + HO2 (yield > 91%) and (2R/S)-3-methyl-1,2-epoxybut-3-ene + OH (yield < 8%). After modest adjustments to ROO(t) and ROO(nt) well-depths (∼0.7 kcal mol−1 each) and barrier height for the transition state associated with the kinetically most dominant channel, R + O2 → isoprene + HO2 (∼2.2 kcal mol−1), the ME model was able to reproduce the experimental findings. Modified Arrhenius expressions for the kinetically important reaction channels are enclosed to facilitate the use of current results in combustion models.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
自己引用率: 10.3%
年間論文数: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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