Influence of Oxygen Atoms and Ring Strain on the Low-Temperature Oxidation Pathways of 1,3-Dioxolane

The Journal of Physical Chemistry A, vol. 127, pp. 2992–2999

Abstract

Biohybrid fuels are a promising solution for making the transportation sector more environmentally friendly. One such interesting fuel candidate is 1,3-dioxolane, which can be produced from inedible biomass. However, very little kinetics data are available for the low-temperature oxidation of this fuel molecule. To remedy this, we present the reaction kinetics of O 2 addition to 1,3-dioxolanyl radicals in this work. All energies have been calculated at the DLPNO-CCSD(T)/CBS//B2PLYPD3BJ/6-311+g(d,p) level of theory. Temperature- and pressure-dependent reaction rate constants have been calculated with the RRKM/master equation method. The effects of heterocyclic oxygen atoms and ring strain on the low-temperature oxidation of 1,3-dioxolane are also compared to that of similar fuel molecules containing five heavy atoms: cyclopentane, tetrahydrofuran, and diethyl ether (DEE). The ring-opening β-scission reactions of the dioxolane hydroperoxy species are found to be the most dominant pathways following the oxidation of 1,3-dioxolanyl radicals. The heterocyclic oxygen atoms in 1,3-dioxolane weaken its C–O bonds, which leads to low barrier heights of the ring-opening reactions. Ring strain in 1,3-dioxolane increases the barriers for isomerization reactions of peroxy radicals compared to the similar reactions of DEE, which has a chain structure.

Authors 5

1. Indu Sekhar Roy Aachen Institute of Technical Thermodynamics

   RWTH Aachen University

   Affiliation as printed

   Institute of Technical Thermodynamics, RWTH Aachen University, 52064 Aachen, Germany

2. Malte Döntgen Aachen Shock Wave Laboratory Chair of High Pressure Gas Dynamics

   RWTH Aachen University

   Affiliation as printed

   Chair of High Pressure Gas Dynamics, Shock Wave Laboratory, RWTH Aachen University, 52064 Aachen, Germany

3. Can Huang Aachen Institute of Technical Thermodynamics

   RWTH Aachen University

   Affiliation as printed

   Institute of Technical Thermodynamics, RWTH Aachen University, 52064 Aachen, Germany

4. Wassja A. Kopp Aachen Institute of Technical Thermodynamics

   RWTH Aachen University

   Affiliation as printed

   Institute of Technical Thermodynamics, RWTH Aachen University, 52064 Aachen, Germany

5. Kai O. Leonhard corresponding Aachen Institute of Technical Thermodynamics

   RWTH Aachen University

   Affiliation as printed

   Institute of Technical Thermodynamics, RWTH Aachen University, 52064 Aachen, Germany