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

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:

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)

Publication Date:: Mon Oct 16 00:00:00 EDT 2017

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.

Copy to clipboard


                    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

Copy to clipboard


                    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.

Copy to clipboard


                    
@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}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (Publisher)

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1016/j.combustflame.2017.09.008

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 41 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

Mutagenicity of Polycyclic Aromatic Hydrocarbons and Amines: A Conformational Hypothesis
journal, December 1984

Broyde, S.; Hingerty, B.
Annals of the New York Academy of Sciences, Vol. 435, Issue 1 First Colloqu
DOI: 10.1111/j.1749-6632.1984.tb13746.x

Formation of Naphthalene, Indene, and Benzene from Cyclopentadiene Pyrolysis: A DFT Study
journal, April 2006

Wang, Dong; Violi, Angela; Kim, Do Hyong
The Journal of Physical Chemistry A, Vol. 110, Issue 14
DOI: 10.1021/jp053628a

The Kinetics of the Recombination of Methyl Radicals and Iodine Atoms.
journal, June 1951

Marcus, R. A.; Rice, O. K.
The Journal of Physical Chemistry, Vol. 55, Issue 6
DOI: 10.1021/j150489a013

The Recombination of Propargyl Radicals: Solving the Master Equation
journal, August 2001

Miller, James A.; Klippenstein, Stephen J.
The Journal of Physical Chemistry A, Vol. 105, Issue 30
DOI: 10.1021/jp0102973

Kinetics of ethylcyclohexane pyrolysis and oxidation: An experimental and detailed kinetic modeling study
journal, July 2015

Wang, Zhandong; Zhao, Long; Wang, Yu
Combustion and Flame, Vol. 162, Issue 7
DOI: 10.1016/j.combustflame.2015.03.017

Tropospheric Air Pollution: Ozone, Airborne Toxics, Polycyclic Aromatic Hydrocarbons, and Particles
journal, May 1997

Finlayson-Pitts, B. J.
Science, Vol. 276, Issue 5315
DOI: 10.1126/science.276.5315.1045

Detailed modeling of PAH and soot formation in a laminar premixed benzene/oxygen/argon low-pressure flame
journal, January 2005

Richter, Henning; Granata, Silvia; Green, William H.
Proceedings of the Combustion Institute, Vol. 30, Issue 1
DOI: 10.1016/j.proci.2004.08.088

Kinetic modeling of soot formation with detailed chemistry and physics: laminar premixed flames of C2 hydrocarbons
journal, April 2000

Appel, Jörg; Bockhorn, Henning; Frenklach, Michael
Combustion and Flame, Vol. 121, Issue 1-2
DOI: 10.1016/S0010-2180(99)00135-2

On the kinetics of the C5H5+C5H5 reaction
journal, January 2013

Cavallotti, Carlo; Polino, Daniela
Proceedings of the Combustion Institute, Vol. 34, Issue 1
DOI: 10.1016/j.proci.2012.05.097

Shock Tube Study of High-Temperature Reactions of Cyclopentadiene
journal, January 1996

Roy, Karin; Frank, Peter; Just, Thomas
Israel Journal of Chemistry, Vol. 36, Issue 3
DOI: 10.1002/ijch.199600038

Gas-phase thermolysis of 1,5-hexadiene: the continuous wave carbon dioxide laser-induced reaction and studies of the cyclization pathway
journal, May 1985

McDonald, J. K.; Merritt, J. A.; Alley, B. J.
Journal of the American Chemical Society, Vol. 107, Issue 11
DOI: 10.1021/ja00297a002

Can the C ₅ H ₅ + C ₅ H ₅ → C ₁₀ H ₁₀ → C ₁₀ H ₉ + H/C ₁₀ H ₈ + H ₂ Reaction Produce Naphthalene? An Ab Initio/RRKM Study
journal, September 2009

Mebel, A. M.; Kislov, V. V.
The Journal of Physical Chemistry A, Vol. 113, Issue 36
DOI: 10.1021/jp905931j

Inversion of the Partition Function. II. The Full Steepest‐Descent Method
journal, June 1970

Hoare, M. R.
The Journal of Chemical Physics, Vol. 52, Issue 11
DOI: 10.1063/1.1672846

Group Additive Values for the Gas-Phase Standard Enthalpy of Formation, Entropy and Heat Capacity of Oxygenates
journal, October 2013

Paraskevas, Paschalis D.; Sabbe, Maarten K.; Reyniers, Marie-Françoise
Chemistry - A European Journal, Vol. 19, Issue 48
DOI: 10.1002/chem.201301381

Comparative Test of Approximations for Calculation of Energy-Level Densities
journal, October 1969

Forst, W.; Prášil, Z.
The Journal of Chemical Physics, Vol. 51, Issue 7
DOI: 10.1063/1.1672449

A review of airborne polycyclic aromatic hydrocarbons (PAHs) and their human health effects
journal, October 2013

Kim, Ki-Hyun; Jahan, Shamin Ara; Kabir, Ehsanul
Environment International, Vol. 60
DOI: 10.1016/j.envint.2013.07.019

Kinetics of the cyclopentadiene decay and the recombination of cyclopentadienyl radicals with H-atoms: Enthalpy of formation of the cyclopentadienyl radical
journal, January 2001

Roy, K.; Braun-Unkhoff, M.; Frank, P.
International Journal of Chemical Kinetics, Vol. 33, Issue 12
DOI: 10.1002/kin.10005

A complete basis set model chemistry. VII. Use of the minimum population localization method
journal, April 2000

Montgomery, J. A.; Frisch, M. J.; Ochterski, J. W.
The Journal of Chemical Physics, Vol. 112, Issue 15
DOI: 10.1063/1.481224

The Penetration of a Potential Barrier by Electrons
journal, June 1930

Eckart, Carl
Physical Review, Vol. 35, Issue 11
DOI: 10.1103/PhysRev.35.1303

The gas phase pyrolysis of phenol
journal, July 1989

Lovell, A. B.; Brezinsky, K.; Glassman, I.
International Journal of Chemical Kinetics, Vol. 21, Issue 7
DOI: 10.1002/kin.550210706

Reducing Emissions of Polycyclic Aromatic Hydrocarbons and Greenhouse Gases from Engines Using a Novel Plasma-Enhanced Combustion System
journal, January 2013

Lin, Yuan-Chung; Yang, Po-Ming; Chen, Chung-Bang
Aerosol and Air Quality Research, Vol. 13, Issue 3
DOI: 10.4209/aaqr.2012.10.0281

An Ab Initio G3-Type/Statistical Theory Study of the Formation of Indene in Combustion Flames. II. The Pathways Originating from Reactions of Cyclic C ₅ SpeciesCyclopentadiene and Cyclopentadienyl Radicals
journal, January 2008

Kislov, V. V.; Mebel, A. M.
The Journal of Physical Chemistry A, Vol. 112, Issue 4
DOI: 10.1021/jp077493f

Bond Dissociation Energies of Organic Molecules
journal, April 2003

Blanksby, Stephen J.; Ellison, G. Barney
Accounts of Chemical Research, Vol. 36, Issue 4
DOI: 10.1021/ar020230d

Kinetic and thermodynamic issues in the formation of aromatic compounds in flames of aliphatic fuels
journal, October 1992

Miller, James A.; Melius, Carl F.
Combustion and Flame, Vol. 91, Issue 1
DOI: 10.1016/0010-2180(92)90124-8

Rates, products, and mechanisms in the gas-phase hydrogenolysis of phenol between 922 and 1175 K
journal, May 1989

Manion, Jeffrey A.; Louw, Robert
The Journal of Physical Chemistry, Vol. 93, Issue 9
DOI: 10.1021/j100346a040

Studies in Homogeneous Gas Reactions. I
journal, February 1928

Kassel, L. S.
The Journal of Physical Chemistry, Vol. 32, Issue 2
DOI: 10.1021/j150284a007

Reaction mechanisms in aromatic hydrocarbon formation involving the C5H5 cyclopentadienyl moiety
journal, January 1996

Melius, Carl F.; Colvin, Michael E.; Marinov, Nick M.
Symposium (International) on Combustion, Vol. 26, Issue 1
DOI: 10.1016/S0082-0784(96)80276-1

Temperature and Molecular Size Dependence of the High-Pressure Limit
journal, July 2003

Wong, Bryan M.; Matheu, David M.; Green, William H.
The Journal of Physical Chemistry A, Vol. 107, Issue 32
DOI: 10.1021/jp034165g

A complete basis set model chemistry. VI. Use of density functional geometries and frequencies
journal, February 1999

Montgomery, J. A.; Frisch, M. J.; Ochterski, J. W.
The Journal of Chemical Physics, Vol. 110, Issue 6
DOI: 10.1063/1.477924

Pyrolytic Hydrocarbon Growth from Cyclopentadiene
journal, December 2010

Kim, Do Hyong; Mulholland, James A.; Wang, Dong
The Journal of Physical Chemistry A, Vol. 114, Issue 47
DOI: 10.1021/jp106749k

Inversion of the Partition Function: The First‐Order Steepest‐Descent Method
journal, January 1970

Hoare, M. R.; Ruijgrok, Th. W.
The Journal of Chemical Physics, Vol. 52, Issue 1
DOI: 10.1063/1.1672655

Kinetic Analysis of Complex Chemical Activation and Unimolecular Dissociation Reactions using QRRK Theory and the Modified Strong Collision Approximation
journal, January 2000

Chang, A. Y.; Bozzelli, J. W.; Dean, A. M.
Zeitschrift für Physikalische Chemie, Vol. 214, Issue 11
DOI: 10.1524/zpch.2000.214.11.1533

The Determination of Bond Dissociation Energies by Pyrolytic Methods.
journal, August 1950

Szwarc, M.
Chemical Reviews, Vol. 47, Issue 1
DOI: 10.1021/cr60146a002

Collisional Energy Transfer of Vibrationally Highly Excited Molecules. VI. Energy Dependence of 〈Δ E〉 in Azulene
journal, April 1989

Hippler, H.; Otto, B.; Troe, J.
Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 93, Issue 4
DOI: 10.1002/bbpc.19890930404

The importance of fuel dissociation and propargyl + allyl association for the formation of benzene in a fuel-rich 1-hexene flame
journal, January 2010

Hansen, N.; Li, W.; Law, M. E.
Physical Chemistry Chemical Physics, Vol. 12, Issue 38
DOI: 10.1039/c0cp00241k

Kinetics of the Self Reaction of Cyclopentadienyl Radicals
journal, February 2015

Knyazev, Vadim D.; Popov, Konstantin V.
The Journal of Physical Chemistry A, Vol. 119, Issue 28
DOI: 10.1021/acs.jpca.5b00644

Analysis of Some Reaction Pathways Active during Cyclopentadiene Pyrolysis
journal, March 2012

Cavallotti, Carlo; Polino, Daniela; Frassoldati, Alessio
The Journal of Physical Chemistry A, Vol. 116, Issue 13
DOI: 10.1021/jp212151p

Energy Levels and Thermodynamic Functions for Molecules with Internal Rotation I. Rigid Frame with Attached Tops
journal, July 1942

Pitzer, Kenneth S.; Gwinn, William D.
The Journal of Chemical Physics, Vol. 10, Issue 7
DOI: 10.1063/1.1723744

Predictive Theory for Hydrogen Atom−Hydrocarbon Radical Association Kinetics
journal, June 2005

Harding, Lawrence B.; Georgievskii, Yuri; Klippenstein, Stephen J.
The Journal of Physical Chemistry A, Vol. 109, Issue 21
DOI: 10.1021/jp0508608

Investigation of a New Pathway Forming Naphthalene by the Recombination Reaction of Cyclopentadienyl Radicals
journal, December 2003

Murakami, Yoshinori; Saejung, Taweesak; Ohashi, Chikako
Chemistry Letters, Vol. 32, Issue 12
DOI: 10.1246/cl.2003.1112

The Azulene-to-Naphthalene Rearrangement Revisited: a DFT Study of Intramolecular and Radical-Promoted Mechanisms
journal, May 2003

Alder, Roger W.; East, Stephen P.; Harvey, Jeremy N.
Journal of the American Chemical Society, Vol. 125, Issue 18
DOI: 10.1021/ja029584q

The Formation of Naphthalene, Azulene, and Fulvalene from Cyclic C ₅ Species in Combustion: An Ab Initio/RRKM Study of 9-H-Fulvalenyl (C ₅ H ₅ −C ₅ H ₄ ) Radical Rearrangements ^†
journal, September 2007

Kislov, V. V.; Mebel, A. M.
The Journal of Physical Chemistry A, Vol. 111, Issue 38
DOI: 10.1021/jp0732099

Reaction Mechanism Generator: Automatic construction of chemical kinetic mechanisms
journal, June 2016

Gao, Connie W.; Allen, Joshua W.; Green, William H.
Computer Physics Communications, Vol. 203
DOI: 10.1016/j.cpc.2016.02.013

Detailed modeling of soot particle nucleation and growth
journal, January 1991

Frenklach, Michael; Wang, Hai
Symposium (International) on Combustion, Vol. 23, Issue 1
DOI: 10.1016/S0082-0784(06)80426-1

Formation of polycyclic aromatic hydrocarbons and their growth to soot—a review of chemical reaction pathways
journal, August 2000

Richter, H.; Howard, J. B.
Progress in Energy and Combustion Science, Vol. 26, Issue 4-6
DOI: 10.1016/S0360-1285(00)00009-5

Automatic estimation of pressure-dependent rate coefficients
journal, January 2012

Allen, Joshua W.; Goldsmith, C. Franklin; Green, William H.
Phys. Chem. Chem. Phys., Vol. 14, Issue 3
DOI: 10.1039/C1CP22765C

Mutagenicity of polycyclic aromatic hydrocarbons
journal, January 1977

Brookes, Peter
Mutation Research/Reviews in Genetic Toxicology, Vol. 39, Issue 3-4
DOI: 10.1016/0165-1110(77)90008-2

Mecanismes de fragmentation pyrolytique du phenol et des cresols
journal, January 1974

Cypres, R.; Bettens, B.
Tetrahedron, Vol. 30, Issue 10
DOI: 10.1016/S0040-4020(01)97298-9

Flue gas cleaning in power stations by using electron beam technology. Influence on PAH emissions
journal, March 2007

Callén, M. S.; de la Cruz, M. T.; Marinov, S.
Fuel Processing Technology, Vol. 88, Issue 3
DOI: 10.1016/j.fuproc.2006.10.006

La formation de la plupart des composes aromatiques produits lors de la pyrolyse du phenol, ne fait pas intervenir le carbone porteur de la fonction hydroxyle
journal, January 1975

Cypres, R.; Bettens, B.
Tetrahedron, Vol. 31, Issue 4
DOI: 10.1016/0040-4020(75)80046-9

The effects of equivalence ratio on the formation of polycyclic aromatic hydrocarbons and soot in premixed ethane flames
journal, June 2000

Melton, Tyler R.; Inal, Fikret; Senkan, Selim M.
Combustion and Flame, Vol. 121, Issue 4
DOI: 10.1016/S0010-2180(99)00180-7

The thermal decomposition of 2,5-dimethylfuran
journal, January 2013

Djokic, Marko; Carstensen, Hans-Heinrich; Van Geem, Kevin M.
Proceedings of the Combustion Institute, Vol. 34, Issue 1
DOI: 10.1016/j.proci.2012.05.066

Theories of Unimolecular gas Reactions at low Pressures
journal, July 1927

Rice, Oscar Knefler; Ramsperger, Herman C.
Journal of the American Chemical Society, Vol. 49, Issue 7
DOI: 10.1021/ja01406a001

Formation Mechanisms of Naphthalene and Indene: From the Interstellar Medium to Combustion Flames
journal, January 2017

Mebel, Alexander M.; Landera, Alexander; Kaiser, Ralf I.
The Journal of Physical Chemistry A, Vol. 121, Issue 5
DOI: 10.1021/acs.jpca.6b09735

An experimental and kinetic modeling study of cyclopentadiene pyrolysis: First growth of polycyclic aromatic hydrocarbons
journal, November 2014

Djokic, Marko R.; Van Geem, Kevin M.; Cavallotti, Carlo
Combustion and Flame, Vol. 161, Issue 11
DOI: 10.1016/j.combustflame.2014.04.013

Radical Chemistry in the Thermal Decomposition of Anisole and Deuterated Anisoles: An Investigation of Aromatic Growth
journal, September 2010

Scheer, Adam M.; Mukarakate, Calvin; Robichaud, David J.
The Journal of Physical Chemistry A, Vol. 114, Issue 34
DOI: 10.1021/jp102046p

The pyrolysis of anisole (C6H5OCH3) using a hyperthermal nozzle
journal, October 2001

Friderichsen, Anders V.; Shin, Eun-Jae; Evans, Robert J.
Fuel, Vol. 80, Issue 12
DOI: 10.1016/S0016-2361(01)00059-X

Automated Discovery of Elementary Chemical Reaction Steps Using Freezing String and Berny Optimization Methods
journal, August 2015

Suleimanov, Yury V.; Green, William H.
Journal of Chemical Theory and Computation, Vol. 11, Issue 9
DOI: 10.1021/acs.jctc.5b00407

Comprehensive reaction mechanism for n-butanol pyrolysis and combustion
journal, January 2011

Harper, Michael R.; Van Geem, Kevin M.; Pyl, Steven P.
Combustion and Flame, Vol. 158, Issue 1
DOI: 10.1016/j.combustflame.2010.06.002

Detailed kinetic modeling of autocatalysis in methane pyrolysis
journal, February 1990

Dean, Anthony M.
The Journal of Physical Chemistry, Vol. 94, Issue 4
DOI: 10.1021/j100367a043

Fundamentally-based kinetic model for propene pyrolysis
journal, December 2015

Wang, Kun; Villano, Stephanie M.; Dean, Anthony M.
Combustion and Flame, Vol. 162, Issue 12
DOI: 10.1016/j.combustflame.2015.08.012

Group Additive Values for the Gas-Phase Standard Enthalpy of Formation, Entropy and Heat Capacity of Oxygenates
journal, October 2013

Paraskevas, Paschalis D.; Sabbe, Maarten K.; Reyniers, Marie-Françoise
Chemistry - A European Journal, Vol. 19, Issue 48
DOI: 10.1002/chem.201301381

Cyclopentadienic compounds as intermediates in the thermal degradation of phenols. Kinetics of the thermal decomposition of cyclopentadiene
journal, December 1972

Spielmann, R.; Cramers, C. A.
Chromatographia, Vol. 5, Issue 12
DOI: 10.1007/bf02310746

Mutagenicity of polycyclic aromatic hydrocarbons
journal, January 1977

Brookes, Peter
Mutation Research/Reviews in Genetic Toxicology, Vol. 39, Issue 3-4
DOI: 10.1016/0165-1110(77)90008-2

Reaction Mechanism Generator: Automatic construction of chemical kinetic mechanisms
journal, June 2016

Gao, Connie W.; Allen, Joshua W.; Green, William H.
Computer Physics Communications, Vol. 203
DOI: 10.1016/j.cpc.2016.02.013

The Determination of Bond Dissociation Energies by Pyrolytic Methods.
journal, August 1950

Szwarc, M.
Chemical Reviews, Vol. 47, Issue 1
DOI: 10.1021/cr60146a002

Temperature and Molecular Size Dependence of the High-Pressure Limit
journal, July 2003

Wong, Bryan M.; Matheu, David M.; Green, William H.
The Journal of Physical Chemistry A, Vol. 107, Issue 32
DOI: 10.1021/jp034165g

Formation of Naphthalene, Indene, and Benzene from Cyclopentadiene Pyrolysis: A DFT Study
journal, April 2006

Wang, Dong; Violi, Angela; Kim, Do Hyong
The Journal of Physical Chemistry A, Vol. 110, Issue 14
DOI: 10.1021/jp053628a

Mutagenicity of Polycyclic Aromatic Hydrocarbons and Amines: A Conformational Hypothesis
journal, December 1984

Broyde, S.; Hingerty, B.
Annals of the New York Academy of Sciences, Vol. 435, Issue 1 First Colloqu
DOI: 10.1111/j.1749-6632.1984.tb13746.x

Similar Records in DOE PAGES and OSTI.GOV collections:

Detailed Experimental and Kinetic Modeling Study of Cyclopentadiene Pyrolysis in the Presence of Ethene

Journal Article Vervust, Alexander J. ; Djokic, Marko R. ; Merchant, Shamel S. ; ... - Energy and Fuels

A combined experimental and kinetic modeling study is presented to improve the understanding of the formation of polycyclic aromatic hydrocarbons at pyrolysis conditions. The copyrolysis of cyclopentadiene (CPD) and ethene was studied in a continuous flow tubular reactor at a pressure of 0.17 MPa and a dilution of 1 mol CPD/1 mol ethene/10 mol N₂. The temperature was varied from 873 to 1163 K, resulting in cyclopentadiene conversions between 1 and 92%. Using an automated reaction network generator, RMG, we present an elementary step kinetic model for CPD pyrolysis that accurately predicts the initial formation of aromatic products. The modelmore »« less
Cited by 19
https://doi.org/10.1021/acs.energyfuels.7b03560

Full Text Available
Formation Mechanisms of Naphthalene and Indene: From the Interstellar Medium to Combustion Flames

Journal Article Mebel, Alexander M. ; Landera, Alexander ; Kaiser, Ralf I. - Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

The article addresses the formation mechanisms of naphthalene and indene, which represent prototype polycyclic aromatic hydrocarbons (PAH) carrying two six-membered and one five- plus a six-membered ring. Theoretical studies of the relevant chemical reactions are overviewed in terms of their potential energy surfaces, rate constants, and product branching ratios; these data are compared with experimental measurements in crossed molecular beams and the pyrolytic chemical reactor emulating the extreme conditions in the interstellar medium (ISM) and the combustion-like environment, respectively. The outcome of the reactions potentially producing naphthalene and indene is shown to critically depend on temperature and pressure or collisionmore »« less
Cited by 106
https://doi.org/10.1021/acs.jpca.6b09735

Full Text Available
Reaction mechanisms in aromatic hydrocarbon formation involving the C{sub 5}H{sub 5} cyclopentadienyl moiety

Conference Melius, C F ; Colvin, M E ; Marinov, N M ; ...

The quantum chemical BAC-MP4 and BAC-MP2 methods have been used to investigate the reaction mechanisms leading to polycyclic aromatic hydrocarbon (PAH) ring formation. In particular the authors have determined the elementary reaction steps in the conversion of two cyclopentadienyl radicals to naphthalene. This reaction mechanism is shown to be an extension of the mechanism occurring in the H atom-assisted conversion of fulvene to benzene. The net reaction involves the formation of dihydrofulvalene, which eliminates a hydrogen atom and then rearranges to form naphthalene through a series of ring closures and openings. The importance of forming the {single_bond}CR({center_dot}){single_bond}CHR{single_bond}CR{prime}{double_bond}CR{double_prime}-moiety, which can undergomore »« less
Full Text Available
Formation mechanism of polycyclic aromatic hydrocarbons and fullerenes in premixed benzene flames

Journal Article Richter, H ; Grieco, W J ; Howard, J B - Combustion and Flame

A better understanding of the formation of polycyclic aromatic hydrocarbons (PAH) and fullerenes is of practical interest due to the apparent environmental health effects of many PAH and potential industrial applications of fullerenes. In the present work, a kinetic model describing the growth of PAH up to coronene (C{sub 24}H{sub 12}) and of C{sub 60} and C{sub 70} fullerenes is developed. Comparison of the model predictions with concentration profiles in a nearly sooting low-pressure premixed, laminar, one-dimensional benzene/oxygen/argon flame (equivalence ratio {phi} = 1.8, pressure = 2.67 kPa) measured by Bittner using a molecular beam system coupled to mass spectrometrymore »« less
https://doi.org/10.1016/S0010-2180(99)00032-2
An experimental and kinetic modeling study of the pyrolysis of isoprene, a significant biogenic hydrocarbon in naturally occurring vegetation fires

Journal Article Grajales-González, E. ; Kukkadapu, Goutham ; Nagaraja, Shashank S. ; ... - Combustion and Flame

Isoprene dominates the carbon flux emitted by vegetation and constitutes 40% of non-methane biogenic emissions worldwide. Despite pyrolysis experiments at temperatures above 1000 K showing a link between isoprene combustion and aromatic species formation, comprehensive mechanistic research on isoprene is scarce in the literature. Here, in this work, we carry out an experimental and theoretical study to build, for the first time, a chemical kinetic model describing isoprene pyrolysis. The formation of polycyclic aromatic hydrocarbon (PAH) precursor species, often observed in vegetation fire plumes, is partially explained by isoprene pyrolysis experiments and theoretical modeling. Molecular dynamics (MD) simulations unveil reactionmore »« less
https://doi.org/10.1016/j.combustflame.2022.112206

Full Text Available

Similar Records

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

Abstract

Citation Formats

Mutagenicity of Polycyclic Aromatic Hydrocarbons and Amines: A Conformational Hypothesis journal, December 1984

Formation of Naphthalene, Indene, and Benzene from Cyclopentadiene Pyrolysis: A DFT Study journal, April 2006

The Kinetics of the Recombination of Methyl Radicals and Iodine Atoms. journal, June 1951

The Recombination of Propargyl Radicals: Solving the Master Equation journal, August 2001

Kinetics of ethylcyclohexane pyrolysis and oxidation: An experimental and detailed kinetic modeling study journal, July 2015

Tropospheric Air Pollution: Ozone, Airborne Toxics, Polycyclic Aromatic Hydrocarbons, and Particles journal, May 1997

Detailed modeling of PAH and soot formation in a laminar premixed benzene/oxygen/argon low-pressure flame journal, January 2005

Kinetic modeling of soot formation with detailed chemistry and physics: laminar premixed flames of C2 hydrocarbons journal, April 2000

On the kinetics of the C5H5+C5H5 reaction journal, January 2013

Shock Tube Study of High-Temperature Reactions of Cyclopentadiene journal, January 1996

Gas-phase thermolysis of 1,5-hexadiene: the continuous wave carbon dioxide laser-induced reaction and studies of the cyclization pathway journal, May 1985

Can the C 5 H 5 + C 5 H 5 → C 10 H 10 → C 10 H 9 + H/C 10 H 8 + H 2 Reaction Produce Naphthalene? An Ab Initio/RRKM Study journal, September 2009

Inversion of the Partition Function. II. The Full Steepest‐Descent Method journal, June 1970

Group Additive Values for the Gas-Phase Standard Enthalpy of Formation, Entropy and Heat Capacity of Oxygenates journal, October 2013

Comparative Test of Approximations for Calculation of Energy-Level Densities journal, October 1969

A review of airborne polycyclic aromatic hydrocarbons (PAHs) and their human health effects journal, October 2013

Kinetics of the cyclopentadiene decay and the recombination of cyclopentadienyl radicals with H-atoms: Enthalpy of formation of the cyclopentadienyl radical journal, January 2001

A complete basis set model chemistry. VII. Use of the minimum population localization method journal, April 2000

The Penetration of a Potential Barrier by Electrons journal, June 1930

The gas phase pyrolysis of phenol journal, July 1989

Reducing Emissions of Polycyclic Aromatic Hydrocarbons and Greenhouse Gases from Engines Using a Novel Plasma-Enhanced Combustion System journal, January 2013

An Ab Initio G3-Type/Statistical Theory Study of the Formation of Indene in Combustion Flames. II. The Pathways Originating from Reactions of Cyclic C 5 SpeciesCyclopentadiene and Cyclopentadienyl Radicals journal, January 2008

Bond Dissociation Energies of Organic Molecules journal, April 2003

Kinetic and thermodynamic issues in the formation of aromatic compounds in flames of aliphatic fuels journal, October 1992

Rates, products, and mechanisms in the gas-phase hydrogenolysis of phenol between 922 and 1175 K journal, May 1989

Studies in Homogeneous Gas Reactions. I journal, February 1928

Reaction mechanisms in aromatic hydrocarbon formation involving the C5H5 cyclopentadienyl moiety journal, January 1996

Temperature and Molecular Size Dependence of the High-Pressure Limit journal, July 2003

A complete basis set model chemistry. VI. Use of density functional geometries and frequencies journal, February 1999

Pyrolytic Hydrocarbon Growth from Cyclopentadiene journal, December 2010

Inversion of the Partition Function: The First‐Order Steepest‐Descent Method journal, January 1970

Kinetic Analysis of Complex Chemical Activation and Unimolecular Dissociation Reactions using QRRK Theory and the Modified Strong Collision Approximation journal, January 2000

The Determination of Bond Dissociation Energies by Pyrolytic Methods. journal, August 1950

Collisional Energy Transfer of Vibrationally Highly Excited Molecules. VI. Energy Dependence of 〈Δ E〉 in Azulene journal, April 1989

The importance of fuel dissociation and propargyl + allyl association for the formation of benzene in a fuel-rich 1-hexene flame journal, January 2010

Kinetics of the Self Reaction of Cyclopentadienyl Radicals journal, February 2015

Analysis of Some Reaction Pathways Active during Cyclopentadiene Pyrolysis journal, March 2012

Energy Levels and Thermodynamic Functions for Molecules with Internal Rotation I. Rigid Frame with Attached Tops journal, July 1942

Predictive Theory for Hydrogen Atom−Hydrocarbon Radical Association Kinetics journal, June 2005

Investigation of a New Pathway Forming Naphthalene by the Recombination Reaction of Cyclopentadienyl Radicals journal, December 2003

The Azulene-to-Naphthalene Rearrangement Revisited: a DFT Study of Intramolecular and Radical-Promoted Mechanisms journal, May 2003

The Formation of Naphthalene, Azulene, and Fulvalene from Cyclic C 5 Species in Combustion: An Ab Initio/RRKM Study of 9-H-Fulvalenyl (C 5 H 5 −C 5 H 4 ) Radical Rearrangements † journal, September 2007

Reaction Mechanism Generator: Automatic construction of chemical kinetic mechanisms journal, June 2016

Detailed modeling of soot particle nucleation and growth journal, January 1991

Formation of polycyclic aromatic hydrocarbons and their growth to soot—a review of chemical reaction pathways journal, August 2000

Automatic estimation of pressure-dependent rate coefficients journal, January 2012

Mutagenicity of polycyclic aromatic hydrocarbons journal, January 1977

Mecanismes de fragmentation pyrolytique du phenol et des cresols journal, January 1974

Flue gas cleaning in power stations by using electron beam technology. Influence on PAH emissions journal, March 2007

La formation de la plupart des composes aromatiques produits lors de la pyrolyse du phenol, ne fait pas intervenir le carbone porteur de la fonction hydroxyle journal, January 1975

The effects of equivalence ratio on the formation of polycyclic aromatic hydrocarbons and soot in premixed ethane flames journal, June 2000

The thermal decomposition of 2,5-dimethylfuran journal, January 2013

Theories of Unimolecular gas Reactions at low Pressures journal, July 1927

Formation Mechanisms of Naphthalene and Indene: From the Interstellar Medium to Combustion Flames journal, January 2017

An experimental and kinetic modeling study of cyclopentadiene pyrolysis: First growth of polycyclic aromatic hydrocarbons journal, November 2014

Radical Chemistry in the Thermal Decomposition of Anisole and Deuterated Anisoles: An Investigation of Aromatic Growth journal, September 2010

The pyrolysis of anisole (C6H5OCH3) using a hyperthermal nozzle journal, October 2001

Automated Discovery of Elementary Chemical Reaction Steps Using Freezing String and Berny Optimization Methods journal, August 2015

Comprehensive reaction mechanism for n-butanol pyrolysis and combustion journal, January 2011

Detailed kinetic modeling of autocatalysis in methane pyrolysis journal, February 1990

Fundamentally-based kinetic model for propene pyrolysis journal, December 2015

Group Additive Values for the Gas-Phase Standard Enthalpy of Formation, Entropy and Heat Capacity of Oxygenates journal, October 2013

Cyclopentadienic compounds as intermediates in the thermal degradation of phenols. Kinetics of the thermal decomposition of cyclopentadiene journal, December 1972

Mutagenicity of polycyclic aromatic hydrocarbons journal, January 1977

Reaction Mechanism Generator: Automatic construction of chemical kinetic mechanisms journal, June 2016

The Determination of Bond Dissociation Energies by Pyrolytic Methods. journal, August 1950

Temperature and Molecular Size Dependence of the High-Pressure Limit journal, July 2003

Formation of Naphthalene, Indene, and Benzene from Cyclopentadiene Pyrolysis: A DFT Study journal, April 2006

Mutagenicity of Polycyclic Aromatic Hydrocarbons and Amines: A Conformational Hypothesis journal, December 1984

Mutagenicity of Polycyclic Aromatic Hydrocarbons and Amines: A Conformational Hypothesis
journal, December 1984

Formation of Naphthalene, Indene, and Benzene from Cyclopentadiene Pyrolysis: A DFT Study
journal, April 2006

The Kinetics of the Recombination of Methyl Radicals and Iodine Atoms.
journal, June 1951

The Recombination of Propargyl Radicals: Solving the Master Equation
journal, August 2001

Kinetics of ethylcyclohexane pyrolysis and oxidation: An experimental and detailed kinetic modeling study
journal, July 2015

Tropospheric Air Pollution: Ozone, Airborne Toxics, Polycyclic Aromatic Hydrocarbons, and Particles
journal, May 1997

Detailed modeling of PAH and soot formation in a laminar premixed benzene/oxygen/argon low-pressure flame
journal, January 2005

Kinetic modeling of soot formation with detailed chemistry and physics: laminar premixed flames of C2 hydrocarbons
journal, April 2000

On the kinetics of the C5H5+C5H5 reaction
journal, January 2013

Shock Tube Study of High-Temperature Reactions of Cyclopentadiene
journal, January 1996

Gas-phase thermolysis of 1,5-hexadiene: the continuous wave carbon dioxide laser-induced reaction and studies of the cyclization pathway
journal, May 1985

Can the C ₅ H ₅ + C ₅ H ₅ → C ₁₀ H ₁₀ → C ₁₀ H ₉ + H/C ₁₀ H ₈ + H ₂ Reaction Produce Naphthalene? An Ab Initio/RRKM Study
journal, September 2009

Inversion of the Partition Function. II. The Full Steepest‐Descent Method
journal, June 1970

Group Additive Values for the Gas-Phase Standard Enthalpy of Formation, Entropy and Heat Capacity of Oxygenates
journal, October 2013

Comparative Test of Approximations for Calculation of Energy-Level Densities
journal, October 1969

A review of airborne polycyclic aromatic hydrocarbons (PAHs) and their human health effects
journal, October 2013

Kinetics of the cyclopentadiene decay and the recombination of cyclopentadienyl radicals with H-atoms: Enthalpy of formation of the cyclopentadienyl radical
journal, January 2001

A complete basis set model chemistry. VII. Use of the minimum population localization method
journal, April 2000

The Penetration of a Potential Barrier by Electrons
journal, June 1930

The gas phase pyrolysis of phenol
journal, July 1989

Reducing Emissions of Polycyclic Aromatic Hydrocarbons and Greenhouse Gases from Engines Using a Novel Plasma-Enhanced Combustion System
journal, January 2013

An Ab Initio G3-Type/Statistical Theory Study of the Formation of Indene in Combustion Flames. II. The Pathways Originating from Reactions of Cyclic C ₅ SpeciesCyclopentadiene and Cyclopentadienyl Radicals
journal, January 2008

Bond Dissociation Energies of Organic Molecules
journal, April 2003

Kinetic and thermodynamic issues in the formation of aromatic compounds in flames of aliphatic fuels
journal, October 1992

Rates, products, and mechanisms in the gas-phase hydrogenolysis of phenol between 922 and 1175 K
journal, May 1989

Studies in Homogeneous Gas Reactions. I
journal, February 1928

Reaction mechanisms in aromatic hydrocarbon formation involving the C5H5 cyclopentadienyl moiety
journal, January 1996

Temperature and Molecular Size Dependence of the High-Pressure Limit
journal, July 2003

A complete basis set model chemistry. VI. Use of density functional geometries and frequencies
journal, February 1999

Pyrolytic Hydrocarbon Growth from Cyclopentadiene
journal, December 2010

Inversion of the Partition Function: The First‐Order Steepest‐Descent Method
journal, January 1970

Kinetic Analysis of Complex Chemical Activation and Unimolecular Dissociation Reactions using QRRK Theory and the Modified Strong Collision Approximation
journal, January 2000

The Determination of Bond Dissociation Energies by Pyrolytic Methods.
journal, August 1950

Collisional Energy Transfer of Vibrationally Highly Excited Molecules. VI. Energy Dependence of 〈Δ E〉 in Azulene
journal, April 1989

The importance of fuel dissociation and propargyl + allyl association for the formation of benzene in a fuel-rich 1-hexene flame
journal, January 2010

Kinetics of the Self Reaction of Cyclopentadienyl Radicals
journal, February 2015

Analysis of Some Reaction Pathways Active during Cyclopentadiene Pyrolysis
journal, March 2012

Energy Levels and Thermodynamic Functions for Molecules with Internal Rotation I. Rigid Frame with Attached Tops
journal, July 1942

Predictive Theory for Hydrogen Atom−Hydrocarbon Radical Association Kinetics
journal, June 2005

Investigation of a New Pathway Forming Naphthalene by the Recombination Reaction of Cyclopentadienyl Radicals
journal, December 2003

The Azulene-to-Naphthalene Rearrangement Revisited: a DFT Study of Intramolecular and Radical-Promoted Mechanisms
journal, May 2003

The Formation of Naphthalene, Azulene, and Fulvalene from Cyclic C ₅ Species in Combustion: An Ab Initio/RRKM Study of 9-H-Fulvalenyl (C ₅ H ₅ −C ₅ H ₄ ) Radical Rearrangements ^†
journal, September 2007

Reaction Mechanism Generator: Automatic construction of chemical kinetic mechanisms
journal, June 2016

Detailed modeling of soot particle nucleation and growth
journal, January 1991

Formation of polycyclic aromatic hydrocarbons and their growth to soot—a review of chemical reaction pathways
journal, August 2000

Automatic estimation of pressure-dependent rate coefficients
journal, January 2012

Mutagenicity of polycyclic aromatic hydrocarbons
journal, January 1977

Mecanismes de fragmentation pyrolytique du phenol et des cresols
journal, January 1974

Flue gas cleaning in power stations by using electron beam technology. Influence on PAH emissions
journal, March 2007

La formation de la plupart des composes aromatiques produits lors de la pyrolyse du phenol, ne fait pas intervenir le carbone porteur de la fonction hydroxyle
journal, January 1975

The effects of equivalence ratio on the formation of polycyclic aromatic hydrocarbons and soot in premixed ethane flames
journal, June 2000

The thermal decomposition of 2,5-dimethylfuran
journal, January 2013

Theories of Unimolecular gas Reactions at low Pressures
journal, July 1927

Formation Mechanisms of Naphthalene and Indene: From the Interstellar Medium to Combustion Flames
journal, January 2017

An experimental and kinetic modeling study of cyclopentadiene pyrolysis: First growth of polycyclic aromatic hydrocarbons
journal, November 2014

Radical Chemistry in the Thermal Decomposition of Anisole and Deuterated Anisoles: An Investigation of Aromatic Growth
journal, September 2010

The pyrolysis of anisole (C6H5OCH3) using a hyperthermal nozzle
journal, October 2001

Automated Discovery of Elementary Chemical Reaction Steps Using Freezing String and Berny Optimization Methods
journal, August 2015

Comprehensive reaction mechanism for n-butanol pyrolysis and combustion
journal, January 2011

Detailed kinetic modeling of autocatalysis in methane pyrolysis
journal, February 1990

Fundamentally-based kinetic model for propene pyrolysis
journal, December 2015

Group Additive Values for the Gas-Phase Standard Enthalpy of Formation, Entropy and Heat Capacity of Oxygenates
journal, October 2013

Cyclopentadienic compounds as intermediates in the thermal degradation of phenols. Kinetics of the thermal decomposition of cyclopentadiene
journal, December 1972

Mutagenicity of polycyclic aromatic hydrocarbons
journal, January 1977

Reaction Mechanism Generator: Automatic construction of chemical kinetic mechanisms
journal, June 2016

The Determination of Bond Dissociation Energies by Pyrolytic Methods.
journal, August 1950

Temperature and Molecular Size Dependence of the High-Pressure Limit
journal, July 2003

Formation of Naphthalene, Indene, and Benzene from Cyclopentadiene Pyrolysis: A DFT Study
journal, April 2006

Mutagenicity of Polycyclic Aromatic Hydrocarbons and Amines: A Conformational Hypothesis
journal, December 1984