An experimental and theoretical study of the thermal decomposition of C4H6 isomers
Abstract
The chemistry of small unsaturated hydrocarbons, such as 1,3–butadiene (1,3–C4H6), 1,2–butadiene (1,2–C4H6), 2–butyne (2–C4H6) and 1–butyne (1–C4H6), is of central importance to the modeling of combustion systems. These species are important intermediates in combustion processes, and yet their high-temperature chemistry remains poorly understood, with various dissociation and isomerization pathways proposed in the literature. Here we investigate the thermal decompositions of 1,3–C4H6, 1,2–C4H6, 2–C4H6 and 1–C4H6 inside a diaphragmless shock tube, at post shock total pressures of 26–261 Torr and temperatures ranging from 1428–2354 K, using laser schlieren densitometry. The experimental work has been complemented by high-level ab initio calculations, which collectively provide strong evidence that formally direct dissociation is the major channel for pyrolysis of 1,3–C4H6 and 2–C4H6; these paths have not been previously reported but are critical to reconciling the current work and disparate literature reports. The reaction mechanism presented here simulates the current experiments and experimental data from the literature very well. As a result, pressure and temperature dependent rate coefficients are given for the isomerization, formally direct and direct dissociation paths.
- Authors:
-
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Brown Univ., Providence, RI (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States); The Univ. of Chicago, Chicago, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1371560
- 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: 121; Journal Issue: 20; Journal ID: ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Lockhart, James P. A., Goldsmith, C. Franklin, Randazzo, John B., Ruscic, Branko, and Tranter, Robert S.. An experimental and theoretical study of the thermal decomposition of C4H6 isomers. United States: N. p., 2017.
Web. doi:10.1021/acs.jpca.7b01186.
Lockhart, James P. A., Goldsmith, C. Franklin, Randazzo, John B., Ruscic, Branko, & Tranter, Robert S.. An experimental and theoretical study of the thermal decomposition of C4H6 isomers. United States. https://doi.org/10.1021/acs.jpca.7b01186
Lockhart, James P. A., Goldsmith, C. Franklin, Randazzo, John B., Ruscic, Branko, and Tranter, Robert S.. Tue .
"An experimental and theoretical study of the thermal decomposition of C4H6 isomers". United States. https://doi.org/10.1021/acs.jpca.7b01186. https://www.osti.gov/servlets/purl/1371560.
@article{osti_1371560,
title = {An experimental and theoretical study of the thermal decomposition of C4H6 isomers},
author = {Lockhart, James P. A. and Goldsmith, C. Franklin and Randazzo, John B. and Ruscic, Branko and Tranter, Robert S.},
abstractNote = {The chemistry of small unsaturated hydrocarbons, such as 1,3–butadiene (1,3–C4H6), 1,2–butadiene (1,2–C4H6), 2–butyne (2–C4H6) and 1–butyne (1–C4H6), is of central importance to the modeling of combustion systems. These species are important intermediates in combustion processes, and yet their high-temperature chemistry remains poorly understood, with various dissociation and isomerization pathways proposed in the literature. Here we investigate the thermal decompositions of 1,3–C4H6, 1,2–C4H6, 2–C4H6 and 1–C4H6 inside a diaphragmless shock tube, at post shock total pressures of 26–261 Torr and temperatures ranging from 1428–2354 K, using laser schlieren densitometry. The experimental work has been complemented by high-level ab initio calculations, which collectively provide strong evidence that formally direct dissociation is the major channel for pyrolysis of 1,3–C4H6 and 2–C4H6; these paths have not been previously reported but are critical to reconciling the current work and disparate literature reports. The reaction mechanism presented here simulates the current experiments and experimental data from the literature very well. As a result, pressure and temperature dependent rate coefficients are given for the isomerization, formally direct and direct dissociation paths.},
doi = {10.1021/acs.jpca.7b01186},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 20,
volume = 121,
place = {United States},
year = {Tue Apr 25 00:00:00 EDT 2017},
month = {Tue Apr 25 00:00:00 EDT 2017}
}
Web of Science
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