The C2H4O isomers in the oxidation of ethylene

Seifert, Nathan A.; Ruscic, Branko; Sivaramakrishnan, Raghu; Prozument, Kirill

doi:10.1016/j.jms.2023.111847

The C₂H₄O isomers in the oxidation of ethylene

Journal Article · Fri Oct 27 00:00:00 EDT 2023 · Journal of Molecular Spectroscopy

DOI:https://doi.org/10.1016/j.jms.2023.111847· OSTI ID:2477357

Seifert, Nathan A. ^[1]; Ruscic, Branko ^[2]; Sivaramakrishnan, Raghu ^[2]; Prozument, Kirill ^[2]

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

A combined rotational spectroscopy, thermochemistry, and kinetic modeling study explores the mechanism of acetaldehyde (ethanal), vinyl alcohol (ethenol), and ethylene oxide (oxirane) formation in the oxidation of ethylene (ethene). Multiplexed quantitative detection of oxidation intermediates and products exiting a SiO₂/ SiC microreactor at 1700 K is demonstrated with the BrightSpec W-band chirped-pulse Fourier transform millimeter-wave spectrometer. The broadband rotational spectrum contains transitions of formaldehyde (CH₂O), methoxy (CH₃O), methanol (CH₃OH), ketene (CH₂CO), acetaldehyde (CH₃CHO), syn-vinyl alcohol (syn- CH₂CHOH), anti-vinyl alcohol (anti-CH₂CHOH), oxirane (c-CH₂OCH₂), propyne (CH₃CCH), and syn-propanal (syn-CH₃CH₂CHO). We focus on the three C₂H₄O species and deduce their concentration ratio [CH₃CHO]:[CH₂CHOH]:[c-CH₂OCH₂] = 1:0.7(2):0.06(2) by comparing the observed line intensities to those simulated with the PGOPHER software. Detailed thermochemistry of the C₂H₄O isomers and conformers is provided by Active Thermochemical Tables. The observed excess concentrations of vinyl alcohol and oxirane relative to the more stable acetaldehyde compared to the equilibrium ratio at 1700 K (1:0.087:0.000024), point to direct chemical pathways to these higher energy isomers. The mechanism for the formation of the three C₂H₄O isomers is analyzed using a 0-D homogenous reactor kinetics simulation for ethylene oxidation. The ratios of the C₂H₄O isomers concentrations predicted by the kinetic model are compared to the experimental values.

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

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2477357

Alternate ID(s):: OSTI ID: 2368890

Journal Information:: Journal of Molecular Spectroscopy, Journal Name: Journal of Molecular Spectroscopy Vol. 398; ISSN 0022-2852

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (57)

Direct Observation of the Ethyl Radical in the Pyrolysis of Ethane Genossar‐Dan, Nadav; Atlas, Sharona; Fux, Dana Angewandte Chemie International Edition, Vol. 62, Issue 32 https://doi.org/10.1002/anie.202305881	journal	June 2023
Analysis of isomeric mixtures by molecular rotational resonance spectroscopy Neill, Justin L.; Evangelisti, Luca; Pate, Brooks H. Analytical Science Advances, Vol. 4, Issue 5-6 https://doi.org/10.1002/ansa.202300021	journal	June 2023
Thermochemistry and Kinetic Analysis of the Unimolecular Oxiranyl Radical Dissociation Reaction: A Theoretical Study Wang, Heng; Bozzelli, Joseph W. ChemPhysChem, Vol. 17, Issue 13 https://doi.org/10.1002/cphc.201600152	journal	April 2016
Boundary-Layer Model to Predict Chemically Reacting Flow within Heated, High-Speed, Microtubular Reactors: PREDICTING CHEMICALLY REACTING FLOW WITHIN HEATED, MICROTUBULAR REACTORS Weddle, Peter J.; Karakaya, Canan; Zhu, Huayang International Journal of Chemical Kinetics, Vol. 50, Issue 7 https://doi.org/10.1002/kin.21173	journal	April 2018
Microwave spectroscopic detection of vinyl alcohol, CH2CHOH Saito, Shuji Chemical Physics Letters, Vol. 42, Issue 3 https://doi.org/10.1016/0009-2614(76)80638-0	journal	September 1976
The ground state of ketene Johns, J. W. C.; Stone, J. M. R.; Winnewisser, G. Journal of Molecular Spectroscopy, Vol. 42, Issue 3 https://doi.org/10.1016/0022-2852(72)90227-5	journal	June 1972
Microwave spectrum, dipole moment, and structure of anti-vinyl alcohol Rodler, M. Journal of Molecular Spectroscopy, Vol. 114, Issue 1 https://doi.org/10.1016/0022-2852(85)90332-7	journal	November 1985
Stark effect and isometric groups of nonrigid molecules. Bossert, W.; Ekkers, J.; Bauder, A. Chemical Physics, Vol. 27, Issue 3 https://doi.org/10.1016/0301-0104(78)87147-X	journal	February 1978
Thermochemistry Ruscic, Branko; Bross, David H. Computer Aided Chemical Engineering https://doi.org/10.1016/B978-0-444-64087-1.00001-2	book	June 2019
Reaction kinetics and implications of the decomposition and formation of C2H4O isomers Wang, Xiaodong; Ye, Lili; Zhang, Xiaoyuan Combustion and Flame, Vol. 250 https://doi.org/10.1016/j.combustflame.2023.112634	journal	April 2023
Pseudo-equilibrium geometry of HNO determined by an E-Band CP-FTmmW spectrometer Zaleski, Daniel P.; Prozument, Kirill Chemical Physics Letters, Vol. 680 https://doi.org/10.1016/j.cplett.2017.05.040	journal	July 2017
Torsion–rotation global analysis of the first three torsional states (νt=0, 1, 2) and terahertz database for methanol Xu, Li-Hong; Fisher, J.; Lees, R. M. Journal of Molecular Spectroscopy, Vol. 251, Issue 1-2 https://doi.org/10.1016/j.jms.2008.03.017	journal	September 2008
Spectroscopy of the ground, first and second excited torsional states of acetaldehyde from 0.05 to 1.6THz Smirnov, I. A.; Alekseev, E. A.; Ilyushin, V. V. Journal of Molecular Spectroscopy, Vol. 295 https://doi.org/10.1016/j.jms.2013.11.006	journal	January 2014
The broadband rotational spectrum of fully deuterated acetaldehyde (CD3CDO) in a CW supersonic expansion Zaleski, Daniel P.; Duan, Chuanxi; Carvajal, Miguel Journal of Molecular Spectroscopy, Vol. 342 https://doi.org/10.1016/j.jms.2017.01.010	journal	December 2017
Millimeter and submillimeter wave spectroscopy of propanal Zingsheim, Oliver; Müller, Holger S. P.; Lewen, Frank Journal of Molecular Spectroscopy, Vol. 342 https://doi.org/10.1016/j.jms.2017.07.008	journal	December 2017
Rapid quantification of isomeric and dehalogenated impurities in pharmaceutical raw materials using MRR spectroscopy Neill, Justin L.; Mikhonin, Alexander V.; Chen, Ted Journal of Pharmaceutical and Biomedical Analysis, Vol. 189 https://doi.org/10.1016/j.jpba.2020.113474	journal	September 2020
PGOPHER: A program for simulating rotational, vibrational and electronic spectra Western, Colin M. Journal of Quantitative Spectroscopy and Radiative Transfer, Vol. 186 https://doi.org/10.1016/j.jqsrt.2016.04.010	journal	January 2017
Measuring flow profiles in heated miniature reactors with X-ray fluorescence spectroscopy Tranter, Robert S.; Kastengren, Alan L.; Porterfield, Jessica P. Proceedings of the Combustion Institute, Vol. 36, Issue 3 https://doi.org/10.1016/j.proci.2016.06.104	journal	January 2017
From theoretical reaction dynamics to chemical modeling of combustion Klippenstein, Stephen J. Proceedings of the Combustion Institute, Vol. 36, Issue 1 https://doi.org/10.1016/j.proci.2016.07.100	journal	January 2017
A framework for automatic discovery of chemically termolecular reactions Barbet, Mark C.; McCullough, Kevin; Burke, Michael P. Proceedings of the Combustion Institute, Vol. 37, Issue 1 https://doi.org/10.1016/j.proci.2018.05.002	journal	January 2019
Reference natural gas flames at nominally autoignitive engine-relevant conditions Krisman, Alex; Mounaïm-Rousselle, Christine; Sivaramakrishnan, Raghu Proceedings of the Combustion Institute, Vol. 37, Issue 2 https://doi.org/10.1016/j.proci.2018.06.050	journal	January 2019
Conformer-Specific Desorption in Propanol Ices Probed by Chirped-Pulse Millimeter-Wave Rotational Spectroscopy Borengasser, Quentin; Hager, Travis; Kanaherarachchi, Anudha The Journal of Physical Chemistry Letters, Vol. 14, Issue 29 https://doi.org/10.1021/acs.jpclett.3c01468	journal	July 2023
Product Branching in the Low Temperature Reaction of CN with Propyne by Chirped-Pulse Microwave Spectroscopy in a Uniform Supersonic Flow Abeysekera, Chamara; Joalland, Baptiste; Ariyasingha, Nuwandi The Journal of Physical Chemistry Letters, Vol. 6, Issue 9 https://doi.org/10.1021/acs.jpclett.5b00519	journal	April 2015
Time-Resolved Kinetic Chirped-Pulse Rotational Spectroscopy in a Room-Temperature Flow Reactor Zaleski, Daniel P.; Harding, Lawrence B.; Klippenstein, Stephen J. The Journal of Physical Chemistry Letters, Vol. 8, Issue 24 https://doi.org/10.1021/acs.jpclett.7b02864	journal	December 2017
Far-Infrared Synchrotron Spectroscopy and Torsional Analysis of the Important Interstellar Molecule, Vinyl Alcohol Bunn, Hayley; Hudson, Rohan J.; Gentleman, Alexander S. ACS Earth and Space Chemistry, Vol. 1, Issue 2 https://doi.org/10.1021/acsearthspacechem.6b00008	journal	February 2017
Astronomical Search of Vinyl Alcohol Assisted by Submillimeter Spectroscopy Melosso, Mattia; McGuire, Brett A.; Tamassia, Filippo ACS Earth and Space Chemistry, Vol. 3, Issue 7 https://doi.org/10.1021/acsearthspacechem.9b00055	journal	June 2019
Flash pyrolytic production of rotationally cold free radicals in a supersonic jet. Resonant multiphoton spectrum of the 3p2A2" .rarw. X2A2" origin band of methyl Chen, Peter; Colson, Steven D.; Chupka, William A. The Journal of Physical Chemistry, Vol. 90, Issue 11 https://doi.org/10.1021/j100402a014	journal	May 1986
Substitution Reactions in the Pyrolysis of Acetone Revealed through a Modeling, Experiment, Theory Paradigm Zaleski, Daniel P.; Sivaramakrishnan, Raghu; Weller, Hailey R. Journal of the American Chemical Society, Vol. 143, Issue 8 https://doi.org/10.1021/jacs.0c11677	journal	February 2021
Toward the Oxidation of the Phenyl Radical and Prevention of PAH Formation in Combustion Systems Parker, Dorian S. N.; Kaiser, Ralf I.; Troy, Tyler P. The Journal of Physical Chemistry A, Vol. 119, Issue 28 https://doi.org/10.1021/jp509170x	journal	November 2014
Chirped-pulse millimeter-wave spectroscopy for dynamics and kinetics studies of pyrolysis reactions Prozument, Kirill; Barratt Park, G.; Shaver, Rachel G. Phys. Chem. Chem. Phys., Vol. 16, Issue 30 https://doi.org/10.1039/C3CP55352C	journal	January 2014
The ozonolysis of isoprene in a cryogenic buffer gas cell by high resolution microwave spectroscopy Porterfield, Jessica P.; Eibenberger, Sandra; Patterson, David Physical Chemistry Chemical Physics, Vol. 20, Issue 24 https://doi.org/10.1039/C8CP02055H	journal	January 2018
High accuracy measurements on the ground state rotational spectrum of formaldehyde (H2CO) up to 2 THzElectronic supplementary information (ESI) available: Newly measured pure rotational transitions. See http://www.rsc.org/suppdata/cp/b3/b301657a/ Brünken, S.; Müller, H. S. P.; Lewen, F. Physical Chemistry Chemical Physics, Vol. 5, Issue 8 https://doi.org/10.1039/b301657a	journal	March 2003
The reaction between propene and hydroxyl Zádor, Judit; Jasper, Ahren W.; Miller, James A. Physical Chemistry Chemical Physics, Vol. 11, Issue 46 https://doi.org/10.1039/b915707g	journal	January 2009
Relative rate study of the addition of HO2 radicals to ethylene and to tetramethylethylene Baldwin, Roy R.; Stout, David R.; Walker, Raymond W. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 80, Issue 12 https://doi.org/10.1039/f19848003481	journal	January 1984
Microwave spectrum, structure, dipole moment and centrifugal distortion of nitrosomethane. Dipole moment of acetaldehyde Turner, Paul H.; Cox, A. Peter Journal of the Chemical Society, Faraday Transactions 2, Vol. 74 https://doi.org/10.1039/f29787400533	journal	January 1978
Intense, hyperthermal source of organic radicals for matrix-isolation spectroscopy Zhang, Xu; Friderichsen, Anders V.; Nandi, Sreela Review of Scientific Instruments, Vol. 74, Issue 6 https://doi.org/10.1063/1.1574397	journal	June 2003
Selective detection of isomers with photoionization mass spectrometry for studies of hydrocarbon flame chemistry Cool, Terrill A.; Nakajima, Koichi; Mostefaoui, Toufik A. The Journal of Chemical Physics, Vol. 119, Issue 16 https://doi.org/10.1063/1.1611173	journal	October 2003
Calculation of Energy Levels for Internal Torsion and Over‐All Rotation. II. CH ₃ CHO Type Molecules; Acetaldehyde Spectra Kilb, R. W.; Lin, Chun Chia; Wilson, E. B. The Journal of Chemical Physics, Vol. 26, Issue 6 https://doi.org/10.1063/1.1743607	journal	June 1957
The Microwave Spectra, Structure, and Dipole Moments of Ethylene Oxide and Ethylene Sulfide Cunningham, George L.; Boyd, A. W.; Myers, Rollie J. The Journal of Chemical Physics, Vol. 19, Issue 6 https://doi.org/10.1063/1.1748331	journal	June 1951
A broadband Fourier transform microwave spectrometer based on chirped pulse excitation Brown, Gordon G.; Dian, Brian C.; Douglass, Kevin O. Review of Scientific Instruments, Vol. 79, Issue 5 https://doi.org/10.1063/1.2919120	journal	May 2008
Design and evaluation of a pulsed-jet chirped-pulse millimeter-wave spectrometer for the 70–102 GHz region Park, G. Barratt; Steeves, Adam H.; Kuyanov-Prozument, Kirill The Journal of Chemical Physics, Vol. 135, Issue 2 https://doi.org/10.1063/1.3597774	journal	July 2011
The microwave spectrum of HO2 near 65 GHz Beers, Yardley; Howard, Carleton J. The Journal of Chemical Physics, Vol. 63, Issue 10 https://doi.org/10.1063/1.431191	journal	November 1975
The microwave spectrum of the methoxy radical CH ₃ O Endo, Yasuki; Saito, Shuji; Hirota, Eizi The Journal of Chemical Physics, Vol. 81, Issue 1 https://doi.org/10.1063/1.447375	journal	July 1984
An optically accessible pyrolysis microreactor Baraban, J. H.; David, D. E.; Ellison, G. Barney Review of Scientific Instruments, Vol. 87, Issue 1 https://doi.org/10.1063/1.4939459	journal	January 2016
Nonthermal rate constants for CH4* + X → CH ₃ + HX, X = H, O, OH, and O ₂ Jasper, Ahren W.; Sivaramakrishnan, Raghu; Klippenstein, Stephen J. The Journal of Chemical Physics, Vol. 150, Issue 11 https://doi.org/10.1063/1.5090394	journal	March 2019
Microwave spectra of molecules of astrophysical interest XV. Propyne Bauer, A.; Boucher, D.; Burie, J. Journal of Physical and Chemical Reference Data, Vol. 8, Issue 2 https://doi.org/10.1063/1.555603	journal	April 1979
Microwave Spectra of Molecules of Astrophysical Interest. XXIII. Acetaldehyde Kleiner, I.; Lovas, F. J.; Godefroid, M. Journal of Physical and Chemical Reference Data, Vol. 25, Issue 4 https://doi.org/10.1063/1.555983	journal	July 1996
Active Thermochemical Tables: the thermophysical and thermochemical properties of methyl, CH ₃ , and methylene, CH ₂ , corrected for nonrigid rotor and anharmonic oscillator effects Ruscic, Branko; Bross, David H. Molecular Physics https://doi.org/10.1080/00268976.2021.1969046	journal	August 2021
The properties of a micro-reactor for the study of the unimolecular decomposition of large molecules Guan, Qi; Urness, Kimberly N.; Ormond, Thomas K. International Reviews in Physical Chemistry, Vol. 33, Issue 4 https://doi.org/10.1080/0144235X.2014.967951	journal	September 2014
Laboratory Microwave Spectrum of Ethylene Oxide Hirose, Chiaki The Astrophysical Journal, Vol. 189 https://doi.org/10.1086/181487	journal	May 1974
Laboratory Studies on the Formation of Three C ₂ H ₄ O Isomers—Acetaldehyde (CH ₃ CHO), Ethylene Oxide (c‐C ₂ H ₄ O), and Vinyl Alcohol (CH ₂ CHOH)—in Interstellar and Cometary Ices Bennett, Chris J.; Osamura, Yoshihiro; Lebar, Matt D. The Astrophysical Journal, Vol. 634, Issue 1 https://doi.org/10.1086/452618	journal	November 2005
The Far-Infrared Rotational Spectrum of Ethylene Oxide Medcraft, Chris; Thompson, Christopher D.; Robertson, Evan G. The Astrophysical Journal, Vol. 753, Issue 1 https://doi.org/10.1088/0004-637X/753/1/18	journal	June 2012
Active Thermochemical Tables: thermochemistry for the 21st century Ruscic, Branko; Pinzon, Reinhardt E.; Laszewski, Gregor von Journal of Physics: Conference Series, Vol. 16 https://doi.org/10.1088/1742-6596/16/1/078	journal	January 2005
Enols Are Common Intermediates in Hydrocarbon Oxidation Taatjes, C. A. Science, Vol. 308, Issue 5730 https://doi.org/10.1126/science.1112532	journal	June 2005
Structures of Cage, Prism, and Book Isomers of Water Hexamer from Broadband Rotational Spectroscopy Perez, C.; Muckle, M. T.; Zaleski, D. P. Science, Vol. 336, Issue 6083 https://doi.org/10.1126/science.1220574	journal	May 2012
Segmented chirped-pulse Fourier transform submillimeter spectroscopy for broadband gas analysis Neill, Justin L.; Harris, Brent J.; Steber, Amanda L. Optics Express, Vol. 21, Issue 17 https://doi.org/10.1364/OE.21.019743	journal	January 2013
Aerodynamic Simulation on Roof for 3,000 Watt Electric Car With Ansys R1 2022 Modeling Hamidi, Cecep Hamidi; Sunardi, Ade; Ariansyah, Ryan Journal of Global Engineering Research and Science, Vol. 1, Issue 1 https://doi.org/10.56904/jgers.v1i1.6	journal	July 2022

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