Formation of phenanthrene via H–assisted isomerization of 2–ethynylbiphenyl produced in the reaction of phenyl with phenylacetylene

Tuli, Lotefa Binta; Mebel, Alexander M.

doi:10.1002/kin.21406

Formation of phenanthrene via H–assisted isomerization of 2–ethynylbiphenyl produced in the reaction of phenyl with phenylacetylene

Journal Article · Tue Aug 04 00:00:00 EDT 2020 · International Journal of Chemical Kinetics

DOI:https://doi.org/10.1002/kin.21406· OSTI ID:1766440

Tuli, Lotefa Binta ^[1]; ^[2]

Florida International Univ., Miami, FL (United States); Florida International University
Florida International Univ., Miami, FL (United States)

Model chemistry G3(MP2,CC)//B3LYP/6–311G(d,p) calculations of the potential energy surface for the reaction of phenyl radical (C₆H₅) with phenylacetylene (C₈H₆) have been carried out and combined with Rice–Ramsperger–Kassel–Marcus/Master Equation calculations of temperature– and pressure–dependent rate constants. The results showed that the reaction can serve as a viable source for the formation of phenanthrene via an indirect route involving a primary reaction of phenyl addition to the ortho carbon in the ring of phenylacetylene and H elimination producing 2–ethynylbiphenyl followed by secondary H–assisted isomerization of 2–ethynylbiphenyl to phenanthrene. In the secondary reaction, the H atom adds to the α carbon of the ethynyl side chain, then a six–member ring closure takes place followed by aromatization via an H loss. The channel of H addition to the side chain of 2–ethynylbiphenyl appears to be much faster than H addition to the ortho carbon in the ethynyl–substituted ring leading back to the initial C₆H₅ + C₈H₆ reactants. Rate constants for the primary C₆H₅ + C₈H₆⇌2–ethynylbiphenyl (p1) + H and secondary p1 + H⇌phenanthrene (p2) + H reactions have been computed in the temperature range of 500–2500 K at pressures of 30 Torr, 1, 10, and 100 atm and fitted to modified Arrhenius expressions. Here, the suggested kinetic scheme and rate constants are proposed as a prototype for the modeling of the growth of polycyclic aromatic hydrocarbons via the phenyl addition–dehydrocyclization (PAC) mechanism involving an addition of a PAH radical to an ethynyl–substituted PAH molecule.

View Accepted Manuscript (DOE)

Research Organization:: Florida International Univ., Miami, FL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: FG02-04ER15570

OSTI ID:: 1766440

Journal Information:: International Journal of Chemical Kinetics, Journal Name: International Journal of Chemical Kinetics Journal Issue: 12 Vol. 52; ISSN 0538-8066

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (52)

Hydrogen Abstraction/Acetylene Addition Revealed Parker, Dorian S. N.; Kaiser, Ralf I.; Troy, Tyler P. Angewandte Chemie International Edition, Vol. 53, Issue 30 https://doi.org/10.1002/anie.201404537	journal	June 2014
Unexpected Chemistry from the Reaction of Naphthyl and Acetylene at Combustion-Like Temperatures Parker, Dorian S. N.; Kaiser, Ralf. I.; Bandyopadhyay, Biswajit Angewandte Chemie International Edition, Vol. 54, Issue 18 https://doi.org/10.1002/anie.201411987	journal	March 2015
Hydrogen-Abstraction/Acetylene-Addition Exposed Yang, Tao; Troy, Tyler P.; Xu, Bo Angewandte Chemie International Edition, Vol. 55, Issue 48 https://doi.org/10.1002/anie.201607509	journal	October 2016
HACA's Heritage: A Free-Radical Pathway to Phenanthrene in Circumstellar Envelopes of Asymptotic Giant Branch Stars Yang, Tao; Kaiser, Ralf I.; Troy, Tyler P. Angewandte Chemie International Edition, Vol. 56, Issue 16 https://doi.org/10.1002/anie.201701259	journal	March 2017
Synthesis of Polycyclic Aromatic Hydrocarbons by Phenyl Addition-Dehydrocyclization: The Third Way Zhao, Long; Prendergast, Matthew B.; Kaiser, Ralf I. Angewandte Chemie International Edition, Vol. 58, Issue 48 https://doi.org/10.1002/anie.201909876	journal	October 2019
A Unified Mechanism on the Formation of Acenes, Helicenes, and Phenacenes in the Gas Phase Zhao, Long; Kaiser, Ralf I.; Xu, Bo Angewandte Chemie International Edition, Vol. 59, Issue 10 https://doi.org/10.1002/anie.201913037	journal	January 2020
Gas‐Phase Synthesis of Triphenylene (C ₁₈ H ₁₂ ) Zhao, Long; Xu, Bo; Ablikim, Utuq ChemPhysChem, Vol. 20, Issue 6 https://doi.org/10.1002/cphc.201801154	journal	February 2019
Gaussian-3 theory using coupled cluster energies Curtiss, Larry A.; Raghavachari, Krishnan; Redfern, Paul C. Chemical Physics Letters, Vol. 314, Issue 1-2 https://doi.org/10.1016/S0009-2614(99)01126-4	journal	November 1999
Kinetic modeling of soot formation with detailed chemistry and physics: laminar premixed flames of C2 hydrocarbons Appel, Jörg; Bockhorn, Henning; Frenklach, Michael Combustion and Flame, Vol. 121, Issue 1-2 https://doi.org/10.1016/S0010-2180(99)00135-2	journal	April 2000
Reduced mechanism of soot formation—Applicationto natural gas-fueled diesel combustion Yoshihara, Y.; Kazakov, A.; Wang, H. Symposium (International) on Combustion, Vol. 25, Issue 1 https://doi.org/10.1016/S0082-0784(06)80730-7	journal	January 1994
Carbon formation in the combustion wave Porter, George Symposium (International) on Combustion, Vol. 4, Issue 1 https://doi.org/10.1016/S0082-0784(53)80031-7	journal	January 1953
Detailed kinetic modeling of soot formation in shock-tube pyrolysis of acetylene Frenklach, Michael; Clary, David W.; Gardiner, William C. Symposium (International) on Combustion, Vol. 20, Issue 1 https://doi.org/10.1016/S0082-0784(85)80578-6	journal	January 1985
Effect of fuel structure on pathways to soot Frenklach, Michael; Clary, David W.; Gardiner, William C. Symposium (International) on Combustion, Vol. 21, Issue 1 https://doi.org/10.1016/S0082-0784(88)80337-0	journal	January 1988
Reactions of vinyl and phenyl radicals with ethyne, ethene and benzene Fahr, Askar; Stein, S. E. Symposium (International) on Combustion, Vol. 22, Issue 1 https://doi.org/10.1016/S0082-0784(89)80112-2	journal	January 1989
On the driving force of PAH production Frenklach, Michael Symposium (International) on Combustion, Vol. 22, Issue 1 https://doi.org/10.1016/S0082-0784(89)80117-1	journal	January 1989
Comparative study on the growth mechanisms of PAHs Shukla, Bikau; Koshi, Mitsuo Combustion and Flame, Vol. 158, Issue 2 https://doi.org/10.1016/j.combustflame.2010.09.012	journal	February 2011
A novel route for PAH growth in HACA based mechanisms Shukla, Bikau; Koshi, Mitsuo Combustion and Flame, Vol. 159, Issue 12 https://doi.org/10.1016/j.combustflame.2012.08.007	journal	December 2012
Investigating repetitive reaction pathways for the formation of polycyclic aromatic hydrocarbons in combustion processes Hansen, Nils; Schenk, Marina; Moshammer, Kai Combustion and Flame, Vol. 180 https://doi.org/10.1016/j.combustflame.2016.09.013	journal	June 2017
Growth of polycyclic aromatic hydrocarbons (PAHs) by methyl radicals: Pyrene formation from phenanthrene Georganta, Evgenia; Rahman, Ramees K.; Raj, Abhijeet Combustion and Flame, Vol. 185 https://doi.org/10.1016/j.combustflame.2017.07.011	journal	November 2017
Computational study of polycyclic aromatic hydrocarbons growth by vinylacetylene addition Liu, Peng; Zhang, Yiran; Li, Zepeng Combustion and Flame, Vol. 202 https://doi.org/10.1016/j.combustflame.2019.01.023	journal	April 2019
Kinetic study of the formation of triphenylene from the condensation of C12H10+C6H5 Xiong, Shaozhuan; Li, Jun; Wang, Jingbo Computational and Theoretical Chemistry, Vol. 985 https://doi.org/10.1016/j.comptc.2012.01.023	journal	April 2012
On the formation of ethynylbiphenyl (C14D5H5; C6D5C6H4CCH) isomers in the reaction of D5-phenyl radicals (C6D5; X2A1) with phenylacetylene (C6H5C2H; X1A1) under single collision conditions Parker, Dorian S. N.; Yang, Tao; Kaiser, Ralf I. Chemical Physics Letters, Vol. 595-596 https://doi.org/10.1016/j.cplett.2014.02.013	journal	March 2014
Role of methyl radicals in the growth of PAHs Shukla, Bikau; Miyoshi, Akira; Koshi, Mitsuo Journal of the American Society for Mass Spectrometry, Vol. 21, Issue 4 https://doi.org/10.1016/j.jasms.2009.12.019	journal	April 2010
Hydrogen-assisted isomerizations of fulvene to benzene and of larger cyclic aromatic hydrocarbons Jasper, Ahren W.; Hansen, Nils Proceedings of the Combustion Institute, Vol. 34, Issue 1 https://doi.org/10.1016/j.proci.2012.06.165	journal	January 2013
Temperature- and pressure-dependent rate coefficients for the HACA pathways from benzene to naphthalene Mebel, Alexander M.; Georgievskii, Yuri; Jasper, Ahren W. Proceedings of the Combustion Institute, Vol. 36, Issue 1 https://doi.org/10.1016/j.proci.2016.07.013	journal	January 2017
On the low-temperature limit of HACA Frenklach, Michael; Singh, Ravi I.; Mebel, Alexander M. Proceedings of the Combustion Institute, Vol. 37, Issue 1 https://doi.org/10.1016/j.proci.2018.05.068	journal	January 2019
Formation Mechanisms of Naphthalene and Indene: From the Interstellar Medium to Combustion Flames Mebel, Alexander M.; Landera, Alexander; Kaiser, Ralf I. The Journal of Physical Chemistry A, Vol. 121, Issue 5 https://doi.org/10.1021/acs.jpca.6b09735	journal	January 2017
Theoretical Study of the Reaction Mechanism and Kinetics of the Phenyl + Allyl and Related Benzyl + Vinyl Associations Morozov, Alexander N.; Mebel, Alexander M. The Journal of Physical Chemistry A, Vol. 123, Issue 9 https://doi.org/10.1021/acs.jpca.9b00345	journal	February 2019
Theoretical Study of PAH Growth by Phenylacetylene Addition Li, Zepeng; Liu, Peng; Zhang, Peng The Journal of Physical Chemistry A, Vol. 123, Issue 47 https://doi.org/10.1021/acs.jpca.9b09450	journal	October 2019
Off the Beaten Path: Almost Clean Formation of Indene from the ortho -Benzyne + Allyl Reaction McCabe, Morgan N.; Hemberger, Patrick; Reusch, Engelbert The Journal of Physical Chemistry Letters, Vol. 11, Issue 8 https://doi.org/10.1021/acs.jpclett.0c00374	journal	March 2020
VUV Photoionization Study of the Formation of the Simplest Polycyclic Aromatic Hydrocarbon: Naphthalene (C ₁₀ H ₈ ) Zhao, Long; Kaiser, Ralf I.; Xu, Bo The Journal of Physical Chemistry Letters, Vol. 9, Issue 10 https://doi.org/10.1021/acs.jpclett.8b01020	journal	May 2018
Density Functional Theory Study of the Formation of Naphthalene and Phenanthrene from Reactions of Phenyl with Vinyl- and Phenylacetylene Aguilera-Iparraguirre, Jorge; Klopper, Wim Journal of Chemical Theory and Computation, Vol. 3, Issue 1 https://doi.org/10.1021/ct600255u	journal	December 2006
Soot formation in binary hydrocarbon mixtures Frenklach, M.; Yuan, T.; Ramachandra, M. K. Energy & Fuels, Vol. 2, Issue 4 https://doi.org/10.1021/ef00010a013	journal	July 1988
Formation Mechanism of Polycyclic Aromatic Hydrocarbons beyond the Second Aromatic Ring Kislov, V. V.; Sadovnikov, A. I.; Mebel, A. M. The Journal of Physical Chemistry A, Vol. 117, Issue 23 https://doi.org/10.1021/jp402481y	journal	May 2013
Reformulation and Solution of the Master Equation for Multiple-Well Chemical Reactions Georgievskii, Yuri; Miller, James A.; Burke, Michael P. The Journal of Physical Chemistry A, Vol. 117, Issue 46 https://doi.org/10.1021/jp4060704	journal	May 2013
PAH Growth Initiated by Propargyl Addition: Mechanism Development and Computational Kinetics Raj, Abhijeet; Al Rashidi, Mariam J.; Chung, Suk Ho The Journal of Physical Chemistry A, Vol. 118, Issue 16 https://doi.org/10.1021/jp410704b	journal	April 2014
Gas phase synthesis of [4]-helicene Zhao, Long; Kaiser, Ralf I.; Xu, Bo Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09224-8	journal	April 2019
Pyrene synthesis in circumstellar envelopes and its role in the formation of 2D nanostructures Zhao, Long; Kaiser, Ralf I.; Xu, Bo Nature Astronomy, Vol. 2, Issue 5 https://doi.org/10.1038/s41550-018-0399-y	journal	March 2018
Low-temperature formation of polycyclic aromatic hydrocarbons in Titan’s atmosphere Zhao, Long; Kaiser, Ralf I.; Xu, Bo Nature Astronomy, Vol. 2, Issue 12 https://doi.org/10.1038/s41550-018-0585-y	journal	October 2018
Pressure-dependent rate constants for PAH growth: formation of indene and its conversion to naphthalene Mebel, Alexander M.; Georgievskii, Yuri; Jasper, Ahren W. Faraday Discussions, Vol. 195 https://doi.org/10.1039/C6FD00111D	journal	January 2016
From benzene to naphthalene: direct measurement of reactions and intermediates of phenyl radicals and acetylene Chu, Te-Chun; Buras, Zachary J.; Smith, Mica C. Physical Chemistry Chemical Physics, Vol. 21, Issue 40 https://doi.org/10.1039/C9CP04554F	journal	January 2019
On the mechanism of soot nucleation Frenklach, Michael; Mebel, Alexander M. Physical Chemistry Chemical Physics, Vol. 22, Issue 9 https://doi.org/10.1039/D0CP00116C	journal	January 2020
Theoretical study of the reaction mechanism and kinetics of the phenyl + propargyl association Morozov, Alexander N.; Mebel, Alexander M. Physical Chemistry Chemical Physics, Vol. 22, Issue 13 https://doi.org/10.1039/D0CP00306A	journal	January 2020
Reaction mechanism of soot formation in flames Frenklach, Michael Physical Chemistry Chemical Physics, Vol. 4, Issue 11 https://doi.org/10.1039/b110045a	journal	February 2002
A highly efficient growth mechanism of polycyclic aromatic hydrocarbons Shukla, Bikau; Koshi, Mitsuo Physical Chemistry Chemical Physics, Vol. 12, Issue 10 https://doi.org/10.1039/b919644g	journal	January 2010
Theory of thermal unimolecular reactions at low pressures. I. Solutions of the master equation Troe, J. The Journal of Chemical Physics, Vol. 66, Issue 11 https://doi.org/10.1063/1.433837	journal	June 1977
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Gaussian-3 (G3) theory for molecules containing first and second-row atoms Curtiss, Larry A.; Raghavachari, Krishnan; Redfern, Paul C. The Journal of Chemical Physics, Vol. 109, Issue 18 https://doi.org/10.1063/1.477422	journal	November 1998
Gaussian-3 theory using density functional geometries and zero-point energies Baboul, Anwar G.; Curtiss, Larry A.; Redfern, Paul C. The Journal of Chemical Physics, Vol. 110, Issue 16 https://doi.org/10.1063/1.478676	journal	April 1999
Low temperature formation of naphthalene and its role in the synthesis of PAHs (Polycyclic Aromatic Hydrocarbons) in the interstellar medium Parker, D. S. N.; Zhang, F.; Kim, Y. S. Proceedings of the National Academy of Sciences, Vol. 109, Issue 1 https://doi.org/10.1073/pnas.1113827108	journal	December 2011
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Chemical Kinetics of Soot Particle Growth Harris, S. J.; Weiner, A. M. Annual Review of Physical Chemistry, Vol. 36, Issue 1 https://doi.org/10.1146/annurev.pc.36.100185.000335	journal	October 1985

Similar Records

On the formation of ethynylbiphenyl (C₁₄D₅H₅; C₆D₅C₆H₄CCH) isomers in the reaction of D5-phenyl radicals (C₆D₅; X²A₁) with phenylacetylene (C₆H₅C₂H; X¹A₁) under single collision conditions

Journal Article · Thu Feb 13 19:00:00 EST 2014 · Chemical Physics Letters · OSTI ID:1602777

Transformation of an Embedded Five-Membered Ring in Polycyclic Aromatic Hydrocarbons via the Hydrogen-Abstraction–Acetylene-Addition Mechanism: A Theoretical Study

Journal Article · Mon Apr 19 20:00:00 EDT 2021 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory · OSTI ID:1843940

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Rice‐Ramsperger‐Kassel‐Marcus Master Equation theory
phenanthrene
potential energy surface
rate constants
reaction mechanism

Formation of phenanthrene via H–assisted isomerization of 2–ethynylbiphenyl produced in the reaction of phenyl with phenylacetylene

Citation Formats

References (52)

Similar Records

Related Subjects