Time-resolved quantification of key species and mechanistic insights in low-temperature tetrahydrofuran oxidation

Demireva, Maria; Au, Kendrew; Hansen, Nils; Sheps, Leonid

doi:10.1039/d3cp06227a

Time-resolved quantification of key species and mechanistic insights in low-temperature tetrahydrofuran oxidation

Journal Article · Fri Mar 15 00:00:00 EDT 2024 · Physical Chemistry Chemical Physics

DOI:https://doi.org/10.1039/d3cp06227a· OSTI ID:2589539

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Sandia National Laboratories (SNL-CA), Livermore, CA (United States)

Here, we investigate the kinetics and report the time-resolved concentrations of key chemical species in the oxidation of tetrahydrofuran (THF) at 7500 torr and 450–675 K. Experiments are carried out using high-pressure multiplexed photoionization mass spectrometry (MPIMS) combined with tunable vacuum ultraviolet radiation from the Berkely Lab Advanced Light Source. Intermediates and products are quantified using reference photoionization (PI) cross sections, when available, and constrained by a global carbon balance tracking approach at all experimental temperatures simultaneously for the species without reference cross sections. From carbon balancing, we determine time-resolved concentrations for the ROO˙ and ˙OOQOOH radical intermediates, butanedial, and the combined concentration of ketohydroperoxide (KHP) and unsaturated hydroperoxide (UHP) products stemming from the ˙QOOH + O₂ reaction. Furthermore, we quantify a product that we tentatively assign as fumaraldehyde, which arises from UHP decomposition via H₂O or ˙OH + H loss. The experimentally derived species concentrations are compared with model predictions using the most recent literature THF oxidation mechanism of Fenard et al., (Combust. Flame, 2018, 191, 252–269). Our results indicate that the literature mechanism significantly overestimates THF consumption and the UHP + KHP concentration at our conditions. The model predictions are sensitive to the rate coefficient for the ROO˙ isomerization to ˙QOOH, which is the gateway for radical chain propagating and branching pathways. Comparisons with our recent results for cyclopentane (Demireva et al., Combust. Flame, 2023, 257, 112506) provide insights into the effect of the ether group on reactivity and highlight the need to determine accurate rate coefficients of ROO˙ isomerization and subsequent reactions.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-CA), Livermore, CA (United States)

Sponsoring Organization:: USDOE; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; NA0003525

OSTI ID:: 2589539

Alternate ID(s):: OSTI ID: 2325539
OSTI ID: 2999475

Report Number(s):: SAND--2025-13172J

Journal Information:: Physical Chemistry Chemical Physics, Journal Name: Physical Chemistry Chemical Physics Journal Issue: 13 Vol. 26; ISSN 1463-9076; ISSN 1463-9084

Publisher:: Royal Society of Chemistry (RSC)Copyright Statement

Country of Publication:: United States

Language:: English

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