Thermally Initiated Formation of Criegee Intermediate CH2OO in the Oxidation of Ethane

Saragi, Rizalina Tama; Seifert, Nathan A.; Sivaramakrishnan, Raghu; Prozument, Kirill

doi:10.1021/acs.jpclett.4c02445

Thermally Initiated Formation of Criegee Intermediate CH₂OO in the Oxidation of Ethane

Journal Article · Thu Dec 12 04:00:00 EST 2024 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.4c02445· OSTI ID:2583970

^[1]; Seifert, Nathan A. ^[2]; ^[1]; ^[1]

Argonne National Laboratory (ANL), Argonne, IL (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States); University of New Haven, West Haven, CT (United States)

Criegee intermediates (CIs) play an important role in atmospheric chemistry as a transient source of the OH radical through their formation by the ozonolysis of unsaturated organic compounds. Here, we report thermally initiated formation of the smallest CI (CH₂OO) in the oxidation of ethane (CH₃CH₃) that may be relevant to combustion and flames. The SiO₂/SiC oxidation microreactor is heated to 1800 K and has a short residence time of ∼100 μs. The CH₂OO we observe is likely formed in a lower-temperature region near the microreactor’s exit. Plausible mechanisms for CH₂OO formation and retention under these conditions mediated by methylperoxy (CH₃OO) radicals are discussed. Pure rotational spectra of CH₂OO and other intermediates (HO₂, CH₃CHO, CH₂CHOH, c-CH₂OCH₂, CH₃CH₂CHO, CH₃OOH, and HCOOH) are detected with a chirped-pulse Fourier transform millimeter-wave spectrometer operating in the frequency range of 60–90 GHz. In conclusion, detection occurs in a molecular beam, where the species are supersonically cooled to 5 K.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2583970

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 50 Vol. 15; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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