Solving the riddle of the high-temperature chemistry of 1,3-dioxolane

Wildenberg, Alina; Döntgen, Malte; Roy, Indu Sekhar; Huang, Can; Lefort, Benoîte; Moyne, Luis Le; Kéromnès, Alan; Leonhard, Kai; Heufer, Karl Alexander

doi:10.1016/j.proci.2022.07.194

Cited by 9 publications

(16 citation statements)

References 27 publications

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“…During the reaction, the hydrogen atom moves in between the carbon and oxygen atoms, forming a rather elongated triangular transition state structure. This reaction has been reported to be key for the consumption of dimethoxy- and trimethoxymethane and also for 1,3-dioxolane and thus is in the focus of the present rate calculations.…”

Section: Resultsmentioning

confidence: 91%

“…Migrations from position 2 and position 4/5 are listed separately, but if each position allows for more than one reaction, the corresponding products are listed in the same row. It should be noted that although all of the products shown here are singlet diradicals, for detailed chemical kinetic modeling purposes these diradicals might be replaced by dissociation products, as has been done before …”

Section: Resultsmentioning

confidence: 96%

“…At the lower temperatures, H-atom abstraction reactions via hydrogen radicals mostly produce the two 1,3-dioxolane radicals. At the higher temperatures, however, a significant share of the H-atom abstraction reactions directly produce ring-opening products of these two 1,3-dioxolane radicals, as discussed in detail by Wildenberg et al…”

Section: Resultsmentioning

confidence: 97%

“…Strongly oxygenated hydrocarbons have the potential to be produced from carbon dioxide and green hydrogen and thus have increasingly gained attention in current research. − Recently, 1,3-dioxolane was proposed as potential alternative fuel compound, as it can be produced as a biohybrid fuel . The first kinetic modeling study was published in 2020 and proposed a detailed chemical kinetic model validated against experimentally measured ignition delay times at ϕ = 1.0 for 20 and 40 bar .…”

Section: Introductionmentioning

confidence: 99%

“…The first kinetic modeling study was published in 2020 and proposed a detailed chemical kinetic model validated against experimentally measured ignition delay times at ϕ = 1.0 for 20 and 40 bar . After reconsideration, a new detailed chemical kinetic modeling study found that 1,3-dioxolane is governed by a rather unusual fuel chemistry, which is dominated by a H-atom migration reaction under high-temperature conditions . As this reaction proved to be of central importance for modeling 1,3-dioxolane combustion and current research activities point toward the use of substituted dioxolanes as potential alternative fuels, the present work will focus on predicting the H-atom migration kinetics and other key properties of methyl- and ethyl-substituted dioxolanes.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical Investigation of Key Properties of the Pyrolysis of Methyl, Ethyl, and Dimethyl Dioxolane Isomers

2022

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Cyclic acetals are considered as carbon-neutral fuels that can be produced from biomass and renewable electricity. Recent investigations on 1,3-dioxolane, a five-membered cyclic acetal, revealed that unimolecular decomposition through H-atom migration within the ring governs thermal decomposition. For methyl-and ethyl-substituted dioxolane compounds, very limited information on thermodynamic, transport, bond dissociation, and thermal decomposition properties is available. The present study remedies this lack of information by providing these properties for methyl-, ethyl-, and dimethyl-substituted dioxolanes in a systematic manner. While adding substituents to the dioxolane ring has only a minor effect on the bond dissociation energies, the barrier heights for H-atom migration are clearly affected by the position of the substituents. Notably, the corresponding transition states are preferably in the boat ring configuration. However, two of the substituted dioxolanes do not allow for this configuration because of their respective bonding structures, resulting in larger barrier heights. The properties provided here will aid the detailed chemical kinetic modeling of substituted dioxolane combustion chemistry.

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Section: Resultsmentioning

confidence: 91%

Section: Resultsmentioning

confidence: 96%

Section: Resultsmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Theoretical Investigation of Key Properties of the Pyrolysis of Methyl, Ethyl, and Dimethyl Dioxolane Isomers

2022

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Reaction path identification and validation from molecular dynamics simulations of hydrocarbon pyrolysis

Schmalz,

Kopp,

Goudeli

et al. 2024

Int J of Chemical Kinetics

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Creation of complex chemical mechanisms for hydrocarbon pyrolysis and combustion is challenging due to the large number of species and reactions involved. Reactive molecular dynamics (RMD) enables the simulation of thousands of reactions and the discovery of previously unknown components of the reaction network. However, due to the inherent imprecision of reactive force fields, it is necessary to verify RMD‐obtained reaction paths using more accurate methods such as Density Functional Theory (DFT). We demonstrate a method for identification and confirmation of reaction pathways from RMD that supplement an established mechanism, using the example of benzene formation from n‐heptane and iso‐octane pyrolysis. We establish a validation workflow to extract reaction geometries from RMD and optimize transition states using the Nudged‐Elastic‐Band method on semi‐empirical and quantum mechanical levels of theory. Our findings demonstrate that the widely recognized ReaxFF parameterization, CHO2016, can identify known pathways from a established soot formation mechanism while also indicating new ones. We also show that CHO2016 underestimates hydrogen migration barriers by up to as compared to DFT and can lower activation barriers significantly for spin‐forbidden reactions. This highlights the necessity for validation or potentially even reparametrization of CHO2016.

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Theory and simulation of shock waves freely propagating through monoatomic non-Boltzmann gas

Döntgen

2024

Theor. Comput. Fluid Dyn.

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The effect of non-Boltzmann energy distributions on the free propagation of shock waves through a monoatomic gas is investigated via theory and simulation. First, the non-Boltzmann heat capacity ratio $$\gamma $$ γ , as a key property for describing shock waves, is derived from first principles via microcanonical integration. Second, atomistic molecular dynamics simulations resembling a shock tube setup are used to test the theory. The presented theory provides heat capacity ratios ranging from the well-known $$\gamma = 5/3$$ γ = 5 / 3 for Boltzmann energy-distributed gas to $$\gamma \rightarrow 1$$ γ → 1 for delta energy-distributed gas. The molecular dynamics simulations of Boltzmann and non-Boltzmann driven gases suggest that the shock wave propagates about 9% slower through the non-Boltzmann driven gas, while the contact wave appears to be about 4% faster if it trails non-Boltzmann driven gas. The observed slowdown of the shock wave through applying a non-Boltzmann energy distribution was found to be consistent with the classical shock wave equations when applying the non-Boltzmann heat capacity ratio. These fundamental findings provide insights into the behavior of non-Boltzmann gases and might help to improve the understanding of gas dynamical phenomena. Graphical abstract

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Solving the riddle of the high-temperature chemistry of 1,3-dioxolane

Cited by 9 publications

References 27 publications

Theoretical Investigation of Key Properties of the Pyrolysis of Methyl, Ethyl, and Dimethyl Dioxolane Isomers

Theoretical Investigation of Key Properties of the Pyrolysis of Methyl, Ethyl, and Dimethyl Dioxolane Isomers

Reaction path identification and validation from molecular dynamics simulations of hydrocarbon pyrolysis

Theory and simulation of shock waves freely propagating through monoatomic non-Boltzmann gas

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