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Title: 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. 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 C 10H 10 species is observed to live long enough to undergo H abstraction reactions to enter the C 10H 9 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:
 [1];  [2];  [3];  [4]; ORCiD logo [4];  [4];  [4]; ORCiD logo [1]
  1. Massachusetts Institute of Technology, Cambridge, MA (United States). Department of Chemical Engineering
  2. ExxonMobil Research and Engineering, Annandale, N.J. (United States).
  3. SABIC, Geleen Technology Center, Urmonderbaan (The Netherlands).
  4. Ghent University, Technologiepark (Belgium). Laboratory for Chemical Technology
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Combustion Energy Frontier Research Center (CEFRC); Lawrence Berkeley National Laboratory, Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC).
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR) (SC-21)
OSTI Identifier:
1462688
DOE Contract Number:  
SC0001198; SC0014901; AC02-05CH11231
Resource Type:
Journal Article
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

Citation Formats

Long, Alan E., Merchant, Shamel S., Vandeputte, A�ron 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., 2018. Web. doi:10.1016/j.combustflame.2017.09.008.
Long, Alan E., Merchant, Shamel S., Vandeputte, A�ron 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. doi:10.1016/j.combustflame.2017.09.008.
Long, Alan E., Merchant, Shamel S., Vandeputte, A�ron 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. doi:10.1016/j.combustflame.2017.09.008.
@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, A�ron 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. 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},
issn = {0010-2180},
number = C,
volume = 187,
place = {United States},
year = {2018},
month = {1}
}