Pressure dependent kinetic analysis of pathways to naphthalene from cyclopentadienyl recombination
Abstract
Cyclopentadiene (CPD) and cyclopentadienyl radical (CPDyl) reactions are known to provide fast routes to naphthalene and other polycyclic aromatic hydrocarbon (PAH) precursors in many systems. In this work, we combine literature quantum chemical pathways for the CPDyl + CPDyl recombination reaction and provide pressure dependent rate coefficient calculations and analysis. Here we find that the simplified 1-step global reaction leading to naphthalene and two H atoms used in many kinetic models is not an adequate description of this chemistry at conditions of relevance to pyrolysis and steam cracking. The C10H10 species is observed to live long enough to undergo H abstraction reactions to enter the C10H9 potential energy surface (PES). Rate coefficient expressions as functions of T and P are reported in CHEMKIN format for future use in kinetic modeling.
- Authors:
-
- Massachusetts Institute of Technology (MIT), Cambridge, MA (United States)
- ExxonMobil Research and Engineering, Annandale, NJ (United States)
- Geleen Technology Center (SABIC), Geleen (Netherlands)
- Ghent University (Belgium)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory, Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Ghent University; European Research Council (ERC)
- OSTI Identifier:
- 1462688
- Alternate Identifier(s):
- OSTI ID: 1547100
- Grant/Contract Number:
- SC0001198; SC0014901; AC02-05CH11231; 290793
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Combustion and Flame
- Additional Journal Information:
- Journal Volume: 187; Journal Issue: C; Journal ID: ISSN 0010-2180
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; polycyclic aromatic hydrocarbons; PAH; cyclopentadiene; naphthalene; pressure dependent kinetics
Citation Formats
Long, Alan E., Merchant, Shamel S., Vandeputte, Aäron G., Carstensen, Hans-Heinrich, Vervust, Alexander J., Marin, Guy B., Van Geem, Kevin M., and Green, William H. Pressure dependent kinetic analysis of pathways to naphthalene from cyclopentadienyl recombination. United States: N. p., 2017.
Web. doi:10.1016/j.combustflame.2017.09.008.
Long, Alan E., Merchant, Shamel S., Vandeputte, Aäron G., Carstensen, Hans-Heinrich, Vervust, Alexander J., Marin, Guy B., Van Geem, Kevin M., & Green, William H. Pressure dependent kinetic analysis of pathways to naphthalene from cyclopentadienyl recombination. United States. https://doi.org/10.1016/j.combustflame.2017.09.008
Long, Alan E., Merchant, Shamel S., Vandeputte, Aäron G., Carstensen, Hans-Heinrich, Vervust, Alexander J., Marin, Guy B., Van Geem, Kevin M., and Green, William H. Mon .
"Pressure dependent kinetic analysis of pathways to naphthalene from cyclopentadienyl recombination". United States. https://doi.org/10.1016/j.combustflame.2017.09.008. https://www.osti.gov/servlets/purl/1462688.
@article{osti_1462688,
title = {Pressure dependent kinetic analysis of pathways to naphthalene from cyclopentadienyl recombination},
author = {Long, Alan E. and Merchant, Shamel S. and Vandeputte, Aäron G. and Carstensen, Hans-Heinrich and Vervust, Alexander J. and Marin, Guy B. and Van Geem, Kevin M. and Green, William H.},
abstractNote = {Cyclopentadiene (CPD) and cyclopentadienyl radical (CPDyl) reactions are known to provide fast routes to naphthalene and other polycyclic aromatic hydrocarbon (PAH) precursors in many systems. In this work, we combine literature quantum chemical pathways for the CPDyl + CPDyl recombination reaction and provide pressure dependent rate coefficient calculations and analysis. Here we find that the simplified 1-step global reaction leading to naphthalene and two H atoms used in many kinetic models is not an adequate description of this chemistry at conditions of relevance to pyrolysis and steam cracking. The C10H10 species is observed to live long enough to undergo H abstraction reactions to enter the C10H9 potential energy surface (PES). Rate coefficient expressions as functions of T and P are reported in CHEMKIN format for future use in kinetic modeling.},
doi = {10.1016/j.combustflame.2017.09.008},
journal = {Combustion and Flame},
number = C,
volume = 187,
place = {United States},
year = {Mon Oct 16 00:00:00 EDT 2017},
month = {Mon Oct 16 00:00:00 EDT 2017}
}
Web of Science
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