Kinetic study of reaction C2H5 + HO2 in a photolysis reactor with time-resolved Faraday rotation spectroscopy

Zhong, Hongtao; Yan, Chao; Teng, Chu C.; Ma, Guoming; Wysocki, Gerard; Ju, Yiguang

doi:10.1016/j.proci.2020.07.095

Kinetic study of reaction C₂H₅ + HO₂ in a photolysis reactor with time-resolved Faraday rotation spectroscopy

Journal Article · Wed Oct 14 00:00:00 EDT 2020 · Proceedings of the Combustion Institute

DOI:https://doi.org/10.1016/j.proci.2020.07.095· OSTI ID:1906176

Zhong, Hongtao ^[1]; ^[2]; Teng, Chu C. ^[2]; ^[2]; Wysocki, Gerard ^[2]; Ju, Yiguang ^[2]

Princeton Univ., NJ (United States); Princeton University
Princeton Univ., NJ (United States)

The rate constant and branching ratios of ethyl reaction with hydroperoxyl radical, C₂H₅ + HO₂ (1), a key radical-radical reaction for intermediate temperature combustion chemistry, were measured in situ for the first time in a photolysis Herriott cell by using mid-IR Faraday rotation spectroscopy (FRS) and UV-IR direct absorption spectroscopy (DAS). The microsecond time-resolved diagnostic technique in this work enabled the direct rate measurements of the target reaction at 40 and 80 mbar and reduced the experimental uncertainty considerably. C₂H₅ and HO₂ radicals were generated by the photolysis of (COCl)₂/C₂H₅I/CH₃OH/O₂/He mixture at 266 nm. By direct measurements of the transient profiles of C₂H₅, HO₂ and OH concentrations, the overall rate constant for this reaction at 297 K was determined as k₁(40 mbar) = (3.8 ± 0.8) × 10^–11 cm³ molecule^–1 s^–1 and k₁(80 mbar) = (4.1 ± 1.0) × 10^–11 cm³ molecule^–1 s^–1. As a result, the direct observation of hydroxyl radical (OH) indicated that OH formation channel was the major channel with a branching ratio of 0.8 ± 0.1.

View Accepted Manuscript (DOE)

Research Organization:: Princeton Univ., NJ (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Fusion Energy Sciences (FES)

Grant/Contract Number:: SC0020233

OSTI ID:: 1906176

Alternate ID(s):: OSTI ID: 1777052

Journal Information:: Proceedings of the Combustion Institute, Journal Name: Proceedings of the Combustion Institute Journal Issue: 1 Vol. 38; ISSN 1540-7489

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (21)

Near infrared cw-CRDS coupled to laser photolysis: Spectroscopy and kinetics of the HO2 radical Thiébaud, J.; Fittschen, C. Applied Physics B, Vol. 85, Issue 2-3 https://doi.org/10.1007/s00340-006-2304-0	journal	June 2006
Engine knock predictions using a fully-detailed and a reduced chemical kinetic mechanism Cowart, J. S.; Keck, J. C.; Heywood, J. B. Symposium (International) on Combustion, Vol. 23, Issue 1 https://doi.org/10.1016/S0082-0784(06)80364-4	journal	January 1991
A shock tube study of the rate constants of HO2 and CH3 reactions Hong, Zekai; Davidson, David Frank; Lam, King-Yiu Combustion and Flame, Vol. 159, Issue 10 https://doi.org/10.1016/j.combustflame.2012.04.009	journal	October 2012
Low-temperature multistage warm diffusion flames Yehia, Omar R.; Reuter, Christopher B.; Ju, Yiguang Combustion and Flame, Vol. 195 https://doi.org/10.1016/j.combustflame.2018.03.013	journal	September 2018
The kinetic study of excited singlet oxygen atom O(1D) reactions with acetylene Yan, Chao; Teng, Chu C.; Chen, Timothy Combustion and Flame, Vol. 212 https://doi.org/10.1016/j.combustflame.2019.10.034	journal	February 2020
Detailed chemical kinetic models for the low-temperature combustion of hydrocarbons with application to gasoline and diesel fuel surrogates Battin-Leclerc, F. Progress in Energy and Combustion Science, Vol. 34, Issue 4 https://doi.org/10.1016/j.pecs.2007.10.002	journal	August 2008
Dynamics of cool flames Ju, Yiguang; Reuter, Christopher B.; Yehia, Omar R. Progress in Energy and Combustion Science, Vol. 75 https://doi.org/10.1016/j.pecs.2019.100787	journal	November 2019
Development of a mid-infrared nitrogen dioxide sensor based on Faraday rotation spectroscopy Liu, Kun; Lewicki, Rafał; Tittel, Frank K. Sensors and Actuators B: Chemical, Vol. 237 https://doi.org/10.1016/j.snb.2016.07.020	journal	December 2016
Chemical activation analysis of the reaction of ethyl radical with oxygen Bozzelli, Joseph W.; Dean, Anthony M. The Journal of Physical Chemistry, Vol. 94, Issue 8 https://doi.org/10.1021/j100371a021	journal	April 1990
Reaction of the ethyl radical with oxygen at millitorr pressures at 243-368 K and a study of the Cl + HO2, ethyl + HO2, and HO2 + HO2 reactions Dobis, Otto; Benson, Sidney W. Journal of the American Chemical Society, Vol. 115, Issue 19 https://doi.org/10.1021/ja00072a038	journal	September 1993
Oxalyl ChlorideA Clean Source of Chlorine Atoms for Kinetic Studies Baklanov, Alexey V.; Krasnoperov, Lev N. The Journal of Physical Chemistry A, Vol. 105, Issue 1 https://doi.org/10.1021/jp0019456	journal	December 2000
Introduction to Active Thermochemical Tables: Several “Key” Enthalpies of Formation Revisited ^† Ruscic, Branko; Pinzon, Reinhardt E.; Morton, Melita L. The Journal of Physical Chemistry A, Vol. 108, Issue 45 https://doi.org/10.1021/jp047912y	journal	November 2004
Kinetics of the Reaction C ₂ H ₅ + HO ₂ by Time-Resolved Mass Spectrometry ^† Ludwig, Wiebke; Brandt, Björn; Friedrichs, Gernot The Journal of Physical Chemistry A, Vol. 110, Issue 9 https://doi.org/10.1021/jp0557464	journal	March 2006
Kinetics of the Gas Phase Reaction CH ₃ + HO ₂ Sangwan, Manuvesh; Krasnoperov, Lev N. The Journal of Physical Chemistry A, Vol. 117, Issue 14 https://doi.org/10.1021/jp4000889	journal	March 2013
Enthalpies of Formation and Bond Dissociation Energies of Lower Alkyl Hydroperoxides and Related Hydroperoxy and Alkoxy Radicals Simmie, John M.; Black, Gráinne; Curran, Henry J. The Journal of Physical Chemistry A, Vol. 112, Issue 22 https://doi.org/10.1021/jp711360z	journal	June 2008
Predictive theory for the combination kinetics of two alkyl radicals Klippenstein, Stephen J.; Georgievskii, Yuri; Harding, Lawrence B. Physical Chemistry Chemical Physics, Vol. 8, Issue 10 https://doi.org/10.1039/b515914h	journal	January 2006
Chemical Kinetic Data Base for Combustion Chemistry. Part I. Methane and Related Compounds Tsang, W.; Hampson, R. F. Journal of Physical and Chemical Reference Data, Vol. 15, Issue 3 https://doi.org/10.1063/1.555759	journal	July 1986
A Detailed Chemical Kinetics Simulation of Engine Knock Leppard, William. R. Combustion Science and Technology, Vol. 43, Issue 1-2 https://doi.org/10.1080/00102208508946993	journal	May 1985
Time-resolved wavelength modulation spectroscopy measurements of HO_2 kinetics Taatjes, Craig A.; Oh, Daniel B. Applied Optics, Vol. 36, Issue 24 https://doi.org/10.1364/AO.36.005817	journal	January 1997
Sensitive and selective detection of OH radicals using Faraday rotation spectroscopy at 28 µm Zhao, Weixiong; Wysocki, Gerard; Chen, Weidong Optics Express, Vol. 19, Issue 3 https://doi.org/10.1364/OE.19.002493	journal	January 2011
Theoretical Study of the C2H5 + HO2 Reaction: Mechanism and Kinetics Wu, Nan-Nan; Zhang, Ming-Zhe; Ou-Yang, Shun-Li Molecules, Vol. 23, Issue 8 https://doi.org/10.3390/molecules23081919	journal	August 2018

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemical kinetics
Faraday rotation spectroscopy
Hydroperoxyl radical
Radical-radical reaction
Rate constant

Kinetic study of reaction C2H5 + HO2 in a photolysis reactor with time-resolved Faraday rotation spectroscopy

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Kinetic study of reaction C₂H₅ + HO₂ in a photolysis reactor with time-resolved Faraday rotation spectroscopy