Time-Resolved Measurements and Master Equation Modelling of the Unimolecular Decomposition of CH3OCH2

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Eskola , A J , Blitz , M A , Pilling , M J , Seakins , P W & Shannon , R J 2020 , ' Time-Resolved Measurements and Master Equation Modelling of the Unimolecular Decomposition of CH3OCH2 ' , Zeitschrift für physikalische Chemie , vol. 234 , no. 7-9 , pp. 1233-1250 . https://doi.org/10.1515/zpch-2020-0007

Title: Time-Resolved Measurements and Master Equation Modelling of the Unimolecular Decomposition of CH3OCH2
Author: Eskola, Arrke J.; Blitz, Mark A.; Pilling, Michael J.; Seakins, Paul W.; Shannon, Robin J.
Other contributor: University of Helsinki, Department of Chemistry

Date: 2020-07
Language: eng
Number of pages: 18
Belongs to series: Zeitschrift für physikalische Chemie
ISSN: 0942-9352
DOI: https://doi.org/10.1515/zpch-2020-0007
URI: http://hdl.handle.net/10138/328821
Abstract: 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 x 10(18) 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, Delta E-0,E-1, and the energy transfer parameters, x 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 Delta E-0,E-1 = (112.3 +/- 0.6) kJ mol(-1), and leads to k(1)(infinity)(T) = 2.9 x 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 N-2 energy transfer parameters to be identified and then further MESMER simulations were carried out, where N-2 was the buffer gas, to generate k(1)(T,p) over a wide range of conditions: 300-1000 K and N-2 = 10(12) -10(25) 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 N-2.
Subject: kinetics
low temperature combustion
master equation
methylmethoxy radical
LOW-TEMPERATURE OXIDATION
DIMETHYL ETHER
THERMAL-DECOMPOSITION
REACTION-KINETICS
RATE CONSTANTS
RADICALS
COMBUSTION
MECHANISM
CHLORINE
YIELDS
116 Chemical sciences
114 Physical sciences
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