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Ab Initio Kinetics of Initial Thermal Pyrolysis of Isopropyl Propionate: A Revisited Study.

ABSTRACT: This work reports a detailed mechanism of the initial thermal pyrolysis of isopropyl propionate, (C₂H₅C(=O)OCH(CH₃)₂), an important biodiesel additive/surrogate, for a wide range of T = 500-2000 K and P = 7.6-76 000 Torr. The detailed kinetic behaviors of the title reaction on the potential energy surface constructed at the CBS-QB3 level were investigated using the RRKM-based master equation (RRKM-ME) rate model, including hindered internal rotation (HIR) and tunneling corrections. It is revealed that the C₃H₆ elimination occurring via a six-centered retro-ene transition state is dominant at low temperatures, while the homolytic fission of the C-C bonds becomes more competitive at higher temperatures. The tunneling treatment is found to slightly increase the rate constant at low temperatures (e.g., ∼1.59 times at 563 K), while the HIR treatment, being important at high temperatures, decreases the rate (e.g., by 5.9 times at 2000 K). Showing a good agreement with experiments in low-temperature kinetics, the kinetic model reveals that the pressure effect should be taken into account at high temperatures. Finally, the temperature- and pressure-dependent kinetic mechanism, consisting of the calculated thermodynamic and kinetic data, is provided for further modeling and simulation of any related systems.

SUBMITTER: Mai TV

PROVIDER: S-EPMC8756594 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Molecular photoswitches that are capable of storing solar energy, so-called molecular solar thermal storage systems, are interesting candidates for future renewable energy applications. In this context, substituted norbornadiene-quadricyclane systems have received renewed interest due to recent advances in their synthesis. The optical, thermodynamic, and kinetic properties of these systems can vary dramatically depending on the chosen substituents. The molecular design of optimal compounds therefore requires a detailed understanding of the effect of individual substituents as well as their interplay. Here, we model absorption spectra, potential energy storage, and thermal barriers for back-conversion of several substituted systems using both single-reference (density functional theory using PBE, B3LYP, CAM-B3LYP, M06, M06-2x, and M06-L functionals as well as MP2 calculations) and multireference methods (complete active space techniques). Already the diaryl substituted compound displays a strong red-shift compared to the unsubstituted system, which is shown to result from the extension of the conjugated ?-system upon substitution. Using specific donor/acceptor groups gives rise to a further albeit relatively smaller red-shift. The calculated storage energy is found to be rather insensitive to the specific substituents, although solvent effects are likely to be important and require further study. The barrier for thermal back-conversion exhibits strong multireference character and as a result is noticeably correlated with the red-shift. Two possible reaction paths for the thermal back-conversion of diaryl substituted quadricyclane are identified and it is shown that among the compounds considered the path via the acceptor side is systematically favored. Finally, the present study establishes the basis for high-throughput screening of norbornadiene-quadricyclane compounds as it provides guidelines for the level of accuracy that can be expected for key properties from several different techniques.

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Ab Initio Kinetics of Initial Thermal Pyrolysis of Isopropyl Propionate: A Revisited Study.

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