TY - JOUR
T1 - High-temperature mid-IR absorption spectra and reaction kinetics of 1,3-dioxolane
AU - Adil, Mohammad
AU - Giri, Binod
AU - Mai, Tam V. -T.
AU - Szőri, Milán
AU - Huynh, Lam K.
AU - Farooq, Aamir
N1 - KAUST Repository Item: Exported on 2023-07-14
Acknowledgements: King Abdullah University of Science and Technology (KAUST) supported the research reported in this publication. This work received financial support from Vietnam National Foundation for Science and Technology Development (NAFOSTED) under grant number 104.06-2020.45. We also acknowledge KIFÜ for awarding us HPC access to a resource based in Hungary at Debrecen.
PY - 2023/6/7
Y1 - 2023/6/7
N2 - Cyclic saturated ethers are proposed as alternative fuels for future sustainability. In particular, dioxolanes have been identified as promising biofuel candidates. However, pyrolysis and oxidation of dioxolanes are not well understood. In this work, we measured the temperature-dependent absorption cross-section of 1,3-dioxolane (13DO) in the mid-IR region over 8.4 – 10.5 μm (950 –1190 cm−1). We applied the spectroscopic knowledge to investigate the temperature and pressure dependence of the rate coefficients of the unimolecular decomposition of 13DO over the temperature range of 1000–1400 K and pressures near 0.7 and 2.4 bar. We employed a rapidly tuning MIRcat-QT™ laser in conjugation with a shock tube to carry out high-temperature spectroscopic and pyrolysis measurements. Measured IR spectra of 13DO exhibited a strong temperature dependence. For the kinetic study, we employed the vibrational feature of 13DO near 1120.5 cm−1 to monitor the decay of 13DO quantitatively. The measured rate coefficients did not show any discernible pressure dependence. This indicates that the rate coefficients of the unimolecular decomposition of 13DO are close to the high-pressure limit under the present experimental conditions. In addition, we rationalized the temperature and pressure dependence of the reaction by employing electronic structure/RRKM-ME calculations. Our theoretical model accurately captured the experimental trends of the rate coefficients of the unimolecular decomposition of 13DO.
AB - Cyclic saturated ethers are proposed as alternative fuels for future sustainability. In particular, dioxolanes have been identified as promising biofuel candidates. However, pyrolysis and oxidation of dioxolanes are not well understood. In this work, we measured the temperature-dependent absorption cross-section of 1,3-dioxolane (13DO) in the mid-IR region over 8.4 – 10.5 μm (950 –1190 cm−1). We applied the spectroscopic knowledge to investigate the temperature and pressure dependence of the rate coefficients of the unimolecular decomposition of 13DO over the temperature range of 1000–1400 K and pressures near 0.7 and 2.4 bar. We employed a rapidly tuning MIRcat-QT™ laser in conjugation with a shock tube to carry out high-temperature spectroscopic and pyrolysis measurements. Measured IR spectra of 13DO exhibited a strong temperature dependence. For the kinetic study, we employed the vibrational feature of 13DO near 1120.5 cm−1 to monitor the decay of 13DO quantitatively. The measured rate coefficients did not show any discernible pressure dependence. This indicates that the rate coefficients of the unimolecular decomposition of 13DO are close to the high-pressure limit under the present experimental conditions. In addition, we rationalized the temperature and pressure dependence of the reaction by employing electronic structure/RRKM-ME calculations. Our theoretical model accurately captured the experimental trends of the rate coefficients of the unimolecular decomposition of 13DO.
UR - http://hdl.handle.net/10754/692940
UR - https://linkinghub.elsevier.com/retrieve/pii/S1540748922003005
UR - http://www.scopus.com/inward/record.url?scp=85134804337&partnerID=8YFLogxK
U2 - 10.1016/j.proci.2022.08.019
DO - 10.1016/j.proci.2022.08.019
M3 - Article
SN - 1873-2704
VL - 39
SP - 621
EP - 631
JO - PROCEEDINGS OF THE COMBUSTION INSTITUTE
JF - PROCEEDINGS OF THE COMBUSTION INSTITUTE
IS - 1
ER -