Time-Resolved Measurements and Master Equation Modelling of the Unimolecular Decomposition of CH3OCH2
| Autor: | Paul W. Seakins, Mark A. Blitz, Arrke J. Eskola, Robin J. Shannon, Michael J. Pilling |
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| Přispěvatelé: | Department of Chemistry, Molecular Science |
| Rok vydání: | 2020 |
| Předmět: |
methylmethoxy radical
MECHANISM LOW-TEMPERATURE OXIDATION 116 Chemical sciences Buffer gas DIMETHYL ETHER Analytical chemistry chemistry.chemical_element master equation REACTION-KINETICS 010402 general chemistry 114 Physical sciences 7. Clean energy 01 natural sciences CHLORINE COMBUSTION RATE CONSTANTS Reaction rate constant YIELDS Ab initio quantum chemistry methods RADICALS 0103 physical sciences Physical and Theoretical Chemistry Laser-induced fluorescence Helium Dye laser 010304 chemical physics Thermal decomposition Photodissociation THERMAL-DECOMPOSITION 0104 chemical sciences chemistry kinetics low temperature combustion |
| Zdroj: | Zeitschrift für Physikalische Chemie. 234:1233-1250 |
| ISSN: | 2196-7156 0942-9352 |
| Popis: | The rate coefficient for the unimolecular decomposition of CH3OCH2, k 1, has been measured in time-resolved experiments by monitoring the HCHO product. CH3OCH2 was rapidly and cleanly generated by 248 nm excimer photolysis of oxalyl chloride, (ClCO)2, in an excess of CH3OCH3, and an excimer pumped dye laser tuned to 353.16 nm was used to probe HCHO via laser induced fluorescence. k 1(T,p) was measured over the ranges: 573–673 K and 0.1–4.3 × 1018 molecule cm−3 with a helium bath gas. In addition, some experiments were carried out with nitrogen as the bath gas. Ab initio calculations on CH3OCH2 decomposition were carried out and a transition-state for decomposition to CH3 and H2CO was identified. This information was used in a master equation rate calculation, using the MESMER code, where the zero-point-energy corrected barrier to reaction, ΔE 0,1, and the energy transfer parameters, ⟨ΔEdown⟩ × T n, were the adjusted parameters to best fit the experimental data, with helium as the buffer gas. The data were combined with earlier measurements by Loucks and Laidler (Can J. Chem. 1967, 45, 2767), with dimethyl ether as the third body, reinterpreted using current literature for the rate coefficient for recombination of CH3OCH2. This analysis returned ΔE 0,1 = (112.3 ± 0.6) kJ mol−1, and leads to k 1 ∞ ( T ) = 2.9 × 10 12 $k_{1}^{\infty}(T)=2.9\times{10^{12}}$ (T/300)2.5 exp(−106.8 kJ mol−1/RT). Using this model, limited experiments with nitrogen as the bath gas allowed N2 energy transfer parameters to be identified and then further MESMER simulations were carried out, where N2 was the buffer gas, to generate k 1(T,p) over a wide range of conditions: 300–1000 K and N2 = 1012–1025 molecule cm−3. The resulting k 1(T,p) has been parameterized using a Troe-expression, so that they can be readily be incorporated into combustion models. In addition, k 1(T,p) has been parametrized using PLOG for the buffer gases, He, CH3OCH3 and N2. |
| Databáze: | OpenAIRE |
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