Pressure dependent kinetic analysis of pathways to naphthalene from cyclopentadienyl recombination

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.

doi:10.1016/j.combustflame.2017.09.008

Title: Pressure dependent kinetic analysis of pathways to naphthalene from cyclopentadienyl recombination

Journal Article · Mon Oct 16 00:00:00 EDT 2017 · Combustion and Flame

DOI:https://doi.org/10.1016/j.combustflame.2017.09.008· OSTI ID:1462688

Long, Alan E. ^[1]; Merchant, Shamel S. ^[2]; Vandeputte, Aäron G. ^[3]; Carstensen, Hans-Heinrich ^[4];

^[4]; Marin, Guy B. ^[4]; Van Geem, Kevin M. ^[4];

^[1]

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)

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.

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Research Organization:: 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 Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Ghent University; European Research Council (ERC)

Grant/Contract Number:: SC0001198; SC0014901; AC02-05CH11231; 290793

OSTI ID:: 1462688

Alternate ID(s):: OSTI ID: 1547100

Journal Information:: Combustion and Flame, Vol. 187, Issue C; ISSN 0010-2180

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 41 works

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