Theoretical study of the reaction mechanism and kinetics of the OH + trimethyl orthoformate ((CH3O)3CH) + O2 reaction

Du, Benni; Zhang, Weichao

doi:10.1016/j.comptc.2019.05.009

Cited by 5 publications

(1 citation statement)

References 46 publications

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“…Finally, with the increasing amount of high-level quantum chemical data for OMEs and OME-derived species becoming available in the literature, ,,,,− it would be interesting to compare the estimation methods developed in this work with novel methods, such as machine learning. The performance of kinetic group additivity, which can be seen as a simplified version of machine learning, indicates the potential of machine learning tools such as deep learning.…”

Section: Results and Discussionmentioning

confidence: 99%

Unimolecular Decomposition of 1,3-Dioxetane and 1,3,5-Trioxane Derivatives: Fast and Accurate Estimation of Kinetic Parameters

Dossche,

De Ras,

Thybaut

et al. 2024

Energy Fuels

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Oxymethylene ethers (OMEs) are a high-potential novel type of e-fuel, which could play an important role in the transition toward a sustainable transportation sector. During the low-temperature oxidation of these OMEs, various cyclic ethers, such as 1,3-dioxetane and 1,3,5-trioxane derivatives, can be formed. However, the current lack of accurate reaction rate coefficients for the unimolecular decomposition of these cyclic ethers has been highlighted as an important obstacle in the development of detailed kinetic models for the low-temperature oxidation of larger OME molecules. In this light, a database with quantum chemical results has been constructed consisting of 34 4-membered ring and 34 6-membered ring cyclic ethers representing important functional groups present during the low-temperature oxidation of OMEs. This database has been used for the development of three estimation methods for the reaction rate coefficients, i.e., rate rules, the Evans−Polanyi relationship, and kinetic group additivity. Balancing performance and complexity, these three methods are currently still the most commonly used estimation methods by automatic kinetic model generation tools. Based upon an assessment of the results, kinetic group additivity was found to be the most accurate method, reaching kinetic accuracy, i.e., a maximum deviation of 1 order of magnitude, for all but one of the 4-membered rings and all but four of the 6-membered ring cyclic ethers. Interactions between the terminal end of a substituent and the ring in combination with the relative stability of different isomers have been proposed to be the main reason for the significant variations between the reaction rate coefficients of the various species. The kinetic parameters can be easily used for the development of detailed kinetic models for larger OMEs based on first principles.

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Section: Results and Discussionmentioning

confidence: 99%

Unimolecular Decomposition of 1,3-Dioxetane and 1,3,5-Trioxane Derivatives: Fast and Accurate Estimation of Kinetic Parameters

Dossche,

De Ras,

Thybaut

et al. 2024

Energy Fuels

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Shock tube study of the pyrolysis kinetics of Di- and trimethoxy methane

Döntgen

Fuller

Peukert

et al. 2022

Combustion and Flame

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Oxidation of linear and branched ethers: A comparative flow reactor study of OME2 and trimethoxymethane

Gaiser

Bierkandt

Oßwald

et al. 2023

Proceedings of the Combustion Institute

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Theoretical study of the reaction mechanism and kinetics of the OH + trimethyl orthoformate ((CH3O)3CH) + O2 reaction

Cited by 5 publications

References 46 publications

Unimolecular Decomposition of 1,3-Dioxetane and 1,3,5-Trioxane Derivatives: Fast and Accurate Estimation of Kinetic Parameters

Unimolecular Decomposition of 1,3-Dioxetane and 1,3,5-Trioxane Derivatives: Fast and Accurate Estimation of Kinetic Parameters

Shock tube study of the pyrolysis kinetics of Di- and trimethoxy methane

Oxidation of linear and branched ethers: A comparative flow reactor study of OME2 and trimethoxymethane

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Theoretical study of the reaction mechanism and kinetics of the OH + trimethyl orthoformate ((CH3O)3CH) + O2 reaction

Cited by 5 publications

References 46 publications

Unimolecular Decomposition of 1,3-Dioxetane and 1,3,5-Trioxane Derivatives: Fast and Accurate Estimation of Kinetic Parameters

Unimolecular Decomposition of 1,3-Dioxetane and 1,3,5-Trioxane Derivatives: Fast and Accurate Estimation of Kinetic Parameters

Shock tube study of the pyrolysis kinetics of Di- and trimethoxy methane

Oxidation of linear and branched ethers: A comparative flow reactor study of OME2 and trimethoxymethane

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Theoretical study of the reaction mechanism and kinetics of the OH + trimethyl orthoformate ((CH3O)3CH) + O2 reaction