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Title: Low-Temperature Oxidation of Ethylene by Ozone in a Jet-Stirred Reactor

Abstract

Ethylene oxidation initiated by ozone addition (ozonolysis) is carried out in a jet-stirred reactor from 300-1000 K to explore the kinetic pathways relevant to low-temperature oxidation. The temperature dependencies of species’ mole fractions are quantified using molecular-beam mass spectrometry with electron ionization and single-photon ionization employing tunable synchrotron-generated vacuum-ultraviolet radiation. Upon ozone addition, significant ethylene oxidation is found in the low-temperature regime from 300-600 K. Here, we provide new insights into the ethylene ozonolysis reaction network via identification and quantification of previously elusive intermediates by combining experimental photoionization energy scans and ab initio threshold energy calculations for isomer identification. Specifically, the C2H4+O3 adduct C2H4O3 is identified as a keto-hydroperoxide (hydroperoxy-acetaldehyde, HOOCH2CHO) based on the calculated and experimentally observed ionization energy of 9.80 (±0.05) eV. Quantification using a photoionization cross-section of 5 Mb at 10.5 eV results in 5 ppm at atmospheric conditions which decreases monotonically with temperature until 550 K. Other hydroperoxide species, that contribute in larger amounts to the low-temperature oxidation of C2H4, like H2O2, CH3OOH, and C2H5OOH, are identified and their temperature-dependent mole fractions are reported. The experimental evidence for additional oxygenated species such as methanol, ketene, acetaldehyde, and hydroxy-acetaldehyde suggest multiple active oxidation routes. This experimental investigationmore » closes the gap between ozonolysis at atmospheric and elevated temperature conditions and provides a database for future modeling.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3];  [1]
  1. Princeton Univ., NJ (United States). Dept. of Mechanical and Aerospace Engineering
  2. Sandia National Lab. (SNL-CA), Livermore, CA (United States). Combustion Research Facility
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS)
OSTI Identifier:
1487124
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 122; Journal Issue: 43; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ethylene; jet-stirred reactor; keto-hydroperoxide; low-temperature chemistry; ozone

Citation Formats

Rousso, Aric C., Hansen, Nils, Jasper, Ahren W., and Ju, Yiguang. Low-Temperature Oxidation of Ethylene by Ozone in a Jet-Stirred Reactor. United States: N. p., 2018. Web. https://doi.org/10.1021/acs.jpca.8b06556.
Rousso, Aric C., Hansen, Nils, Jasper, Ahren W., & Ju, Yiguang. Low-Temperature Oxidation of Ethylene by Ozone in a Jet-Stirred Reactor. United States. https://doi.org/10.1021/acs.jpca.8b06556
Rousso, Aric C., Hansen, Nils, Jasper, Ahren W., and Ju, Yiguang. Sun . "Low-Temperature Oxidation of Ethylene by Ozone in a Jet-Stirred Reactor". United States. https://doi.org/10.1021/acs.jpca.8b06556. https://www.osti.gov/servlets/purl/1487124.
@article{osti_1487124,
title = {Low-Temperature Oxidation of Ethylene by Ozone in a Jet-Stirred Reactor},
author = {Rousso, Aric C. and Hansen, Nils and Jasper, Ahren W. and Ju, Yiguang},
abstractNote = {Ethylene oxidation initiated by ozone addition (ozonolysis) is carried out in a jet-stirred reactor from 300-1000 K to explore the kinetic pathways relevant to low-temperature oxidation. The temperature dependencies of species’ mole fractions are quantified using molecular-beam mass spectrometry with electron ionization and single-photon ionization employing tunable synchrotron-generated vacuum-ultraviolet radiation. Upon ozone addition, significant ethylene oxidation is found in the low-temperature regime from 300-600 K. Here, we provide new insights into the ethylene ozonolysis reaction network via identification and quantification of previously elusive intermediates by combining experimental photoionization energy scans and ab initio threshold energy calculations for isomer identification. Specifically, the C2H4+O3 adduct C2H4O3 is identified as a keto-hydroperoxide (hydroperoxy-acetaldehyde, HOOCH2CHO) based on the calculated and experimentally observed ionization energy of 9.80 (±0.05) eV. Quantification using a photoionization cross-section of 5 Mb at 10.5 eV results in 5 ppm at atmospheric conditions which decreases monotonically with temperature until 550 K. Other hydroperoxide species, that contribute in larger amounts to the low-temperature oxidation of C2H4, like H2O2, CH3OOH, and C2H5OOH, are identified and their temperature-dependent mole fractions are reported. The experimental evidence for additional oxygenated species such as methanol, ketene, acetaldehyde, and hydroxy-acetaldehyde suggest multiple active oxidation routes. This experimental investigation closes the gap between ozonolysis at atmospheric and elevated temperature conditions and provides a database for future modeling.},
doi = {10.1021/acs.jpca.8b06556},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 43,
volume = 122,
place = {United States},
year = {2018},
month = {10}
}

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Figures / Tables:

Figure 1 Figure 1: Ethylene ozonolysis reaction pathway with major intermediate species.

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