Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Kinetics and Products of Vinyl + 1,3-Butadiene, a Potential Route to Benzene

Abstract

The reaction between vinyl radical, C2H3, and 1,3-butadiene, 1,3-C4H6, has long been recognized as a potential route to benzene, particularly in 1,3-butadiene flames, but the lack of reliable rate coefficients has hindered assessments of its true contribution. Here, by using laser flash photolysis and visible laser absorbance (λ = 423.2 nm), we measured the overall rate coefficient for C2H3 + 1,3-C4H6, k1, at 297 K ≤ T ≤ 494 K and 4 ≤ P ≤ 100 Torr. k1 was in the high-pressure limit in this range and could be fit by the simple Arrhenius expression k1 = (1.1 ± 0.2) × 10–12 cm3 molecule–1 s–1 exp(–9.9 ± 0.6 kJ mol–1/RT). Using photoionization time-of-flight mass spectrometry, we also investigated the products formed. At T ≤ 494 K and P = 25 Torr, we found only C6H9 adduct species, while at 494 K ≤ T ≤ 700 K and P = 4 Torr, we observed ≤~10% branching to cyclohexadiene in addition to C6H9. Quantum chemistry master-equation calculations using the modified strong collision model indicate that n-C6H9 is the dominant product at low temperature, consistent with our experimental results, and predict the rate coefficient and branching ratios at higher T where chemically activatedmore » channels become important. Predictions of k1 are in close agreement with our experimental results, allowing us to recommend the following modified Arrhenius expression in the high-pressure limit from 300 to 2000 K: k1 = 6.5 × 10–20 cm3 molecule–1 s–1 T2.40 exp(–1.76 kJ mol–1/RT).« less

Authors:
 [1];  [1];  [1];  [2];  [3];  [1]
+ Show Author Affiliations
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  2. Tianjin Univ. (China)
  3. Alexandria Univ. (Egypt)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Combustion Energy Frontier Research Center (CEFRC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); China Scholarship Council; Fulbright Commission and Alexandria Univ.
OSTI Identifier:
1369833
Grant/Contract Number:  
SC0001198; AC02-05CH11231; 201308120042; NCET-13-0408
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 119; Journal Issue: 28; Related Information: CEFRC partners with Princeton University (lead); Argonne National Laboratory; University of Connecticut; Cornell University; Massachusetts Institute of Technology; University of Minnesota; Sandia National Laboratories; University of Southern California; Stanford University; University of Wisconsin, Madison; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Photodissociation; Absorption; Aromatic compounds; Vinyl; Lasers

Citation Formats

Buras, Zachary J., Dames, Enoch E., Merchant, Shamel S., Liu, Guozhu, Elsamra, Rehab M. I., and Green, William H. Kinetics and Products of Vinyl + 1,3-Butadiene, a Potential Route to Benzene. United States: N. p., 2015. Web. doi:10.1021/jp512705r.
Copy to clipboard
Buras, Zachary J., Dames, Enoch E., Merchant, Shamel S., Liu, Guozhu, Elsamra, Rehab M. I., & Green, William H. Kinetics and Products of Vinyl + 1,3-Butadiene, a Potential Route to Benzene. United States. https://doi.org/10.1021/jp512705r
Copy to clipboard
Buras, Zachary J., Dames, Enoch E., Merchant, Shamel S., Liu, Guozhu, Elsamra, Rehab M. I., and Green, William H. Tue . "Kinetics and Products of Vinyl + 1,3-Butadiene, a Potential Route to Benzene". United States. https://doi.org/10.1021/jp512705r. https://www.osti.gov/servlets/purl/1369833.
Copy to clipboard
@article{osti_1369833,
title = {Kinetics and Products of Vinyl + 1,3-Butadiene, a Potential Route to Benzene},
author = {Buras, Zachary J. and Dames, Enoch E. and Merchant, Shamel S. and Liu, Guozhu and Elsamra, Rehab M. I. and Green, William H.},
abstractNote = {The reaction between vinyl radical, C2H3, and 1,3-butadiene, 1,3-C4H6, has long been recognized as a potential route to benzene, particularly in 1,3-butadiene flames, but the lack of reliable rate coefficients has hindered assessments of its true contribution. Here, by using laser flash photolysis and visible laser absorbance (λ = 423.2 nm), we measured the overall rate coefficient for C2H3 + 1,3-C4H6, k1, at 297 K ≤ T ≤ 494 K and 4 ≤ P ≤ 100 Torr. k1 was in the high-pressure limit in this range and could be fit by the simple Arrhenius expression k1 = (1.1 ± 0.2) × 10–12 cm3 molecule–1 s–1 exp(–9.9 ± 0.6 kJ mol–1/RT). Using photoionization time-of-flight mass spectrometry, we also investigated the products formed. At T ≤ 494 K and P = 25 Torr, we found only C6H9 adduct species, while at 494 K ≤ T ≤ 700 K and P = 4 Torr, we observed ≤~10% branching to cyclohexadiene in addition to C6H9. Quantum chemistry master-equation calculations using the modified strong collision model indicate that n-C6H9 is the dominant product at low temperature, consistent with our experimental results, and predict the rate coefficient and branching ratios at higher T where chemically activated channels become important. Predictions of k1 are in close agreement with our experimental results, allowing us to recommend the following modified Arrhenius expression in the high-pressure limit from 300 to 2000 K: k1 = 6.5 × 10–20 cm3 molecule–1 s–1 T2.40 exp(–1.76 kJ mol–1/RT).},
doi = {10.1021/jp512705r},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 28,
volume = 119,
place = {United States},
year = {Tue Apr 28 00:00:00 EDT 2015},
month = {Tue Apr 28 00:00:00 EDT 2015}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/jp512705r
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 20 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

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

An Association between Air Pollution and Mortality in Six U.S. Cities
journal, December 1993

Strong radiative heating due to the mixing state of black carbon in atmospheric aerosols
journal, February 2001

Soot climate forcing via snow and ice albedos
journal, December 2003

  • Hansen, J.; Nazarenko, L.
  • Proceedings of the National Academy of Sciences, Vol. 101, Issue 2
  • DOI: 10.1073/pnas.2237157100

Soot and smoke aerosol may not warm climate: SOOT AND SMOKE AEROSOL MAY NOT WARM CLIMATE
journal, November 2003

  • Penner, Joyce E.; Zhang, Sophia Y.; Chuang, Catherine C.
  • Journal of Geophysical Research: Atmospheres, Vol. 108, Issue D21
  • DOI: 10.1029/2003JD003409

Studies of aromatic hydrocarbon formation mechanisms in flames: Progress towards closing the fuel gap
journal, January 2006

  • McEnally, Charles S.; Pfefferle, Lisa D.; Atakan, Burak
  • Progress in Energy and Combustion Science, Vol. 32, Issue 3
  • DOI: 10.1016/j.pecs.2005.11.003

Formation of nascent soot and other condensed-phase materials in flames
journal, January 2011

Sooting behavior in temperature-controlled laminar diffusion flames
journal, October 1984

Soot formation in combustion processes
journal, January 1989

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

Formation mechanisms of aromatic compounds in aliphatic flames
journal, April 1984

Forming benzene in flames by chemically activated isomerization
journal, December 1989

  • Westmoreland, Phillip R.; Dean, Anthony M.; Howard, Jack B.
  • The Journal of Physical Chemistry, Vol. 93, Issue 25
  • DOI: 10.1021/j100362a008

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

A Theoretical Analysis of the Reaction between Vinyl and Acetylene:  Quantum Chemistry and Solution of the Master Equation
journal, July 2000

  • Miller, James A.; Klippenstein, Stephen J.; Robertson, Struan H.
  • The Journal of Physical Chemistry A, Vol. 104, Issue 32
  • DOI: 10.1021/jp000687+

The Reaction of n - and i -C 4 H 5 Radicals with Acetylene †
journal, May 2007

  • Senosiain, Juan P.; Miller, James A.
  • The Journal of Physical Chemistry A, Vol. 111, Issue 19
  • DOI: 10.1021/jp0675126

Modeling Studies of the Homogeneous Formation of Aromatic Compounds in the Thermal Decomposition of n-Hexane
journal, November 1983

  • Ebert, K. H.; Ederer, H. J.; Stabel, U.
  • Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 87, Issue 11
  • DOI: 10.1002/bbpc.19830871115

Pyrolysis of methyl chloride, a pathway in the chlorine-catalyzed polymerization of methane
journal, April 1984

  • Weissman, Maia; Benson, Sydney W.
  • International Journal of Chemical Kinetics, Vol. 16, Issue 4
  • DOI: 10.1002/kin.550160403

Benene formation chemistry in premixed 1,3-butadiene flames
journal, January 1996

The kinetic modeling of soot precursors in a butadiene flame
journal, August 2000

Quantum Chemistry Computation of Rate Constants for Reactions Involved in the First Aromatic Ring Formation
journal, August 2002

  • Cavallotti, Carlo; Rota, Renato; Carrà, Sergio
  • The Journal of Physical Chemistry A, Vol. 106, Issue 34
  • DOI: 10.1021/jp025922y

A Quantum Chemistry Study of the Formation of pah and soot Precursors Through Butadiene Reactions
journal, May 2004

  • Cavallotti, C.; Fascella, S.; Rota, R.
  • Combustion Science and Technology, Vol. 176, Issue 5-6
  • DOI: 10.1080/00102200490428026

Rich premixed laminar methane flames doped by light unsaturated hydrocarbons
journal, October 2007

Kinetic Modeling of Ethane Pyrolysis at High Conversion
journal, September 2011

  • Xu, Chen; Al Shoaibi, Ahmed Sultan; Wang, Chenguang
  • The Journal of Physical Chemistry A, Vol. 115, Issue 38
  • DOI: 10.1021/jp206503d

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

The Recombination of Propargyl Radicals and Other Reactions on a C 6 H 6 Potential
journal, October 2003

  • Miller, James A.; Klippenstein, Stephen J.
  • The Journal of Physical Chemistry A, Vol. 107, Issue 39
  • DOI: 10.1021/jp030375h

Association rate constants for reactions between resonance-stabilized radicals: C3H3 + C3H3, C3H3 + C3H5, and C3H5 + C3H5
journal, January 2007

  • Georgievskii, Yuri; Miller, James A.; Klippenstein, Stephen J.
  • Physical Chemistry Chemical Physics, Vol. 9, Issue 31
  • DOI: 10.1039/b703261g

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

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

The thermal unimolecular isomerisation of bicyclo[3,1,0]hex-2-ene and decomposition of cyclohexa-1,4-diene
journal, January 1966

  • Ellis, R. J.; Frey, H. M.
  • Journal of the Chemical Society A: Inorganic, Physical, Theoretical
  • DOI: 10.1039/j19660000553

Kinetics and mechanism of the pyrolysis of 1,4-cyclohexadiene
journal, January 1967

Very low pressure pyrolysis of 1,3-cyclohexadiene. Orbital symmetry nonallowed reaction
journal, July 1973

  • Alfassi, Zeev B.; Benson, Sidney W.; Golden, David M.
  • Journal of the American Chemical Society, Vol. 95, Issue 15
  • DOI: 10.1021/ja00796a002

Addition of cyclohexane to slowly reacting H 2 –O 2 mixtures at 480 °C
journal, January 1989

  • Gulati, Suresh K.; Walker, Raymond W.
  • J. Chem. Soc., Faraday Trans. 2, Vol. 85, Issue 11
  • DOI: 10.1039/F29898501799

Real-time observation of concerted benzene formation in the infrared multiphoton dissociation of 1,4-cyclohexadiene
journal, July 1991

Experimental and modeling study of the oxidation of cyclohexene
journal, January 2003

  • Dayma, G.; Glaude, P. A.; Fournet, R.
  • International Journal of Chemical Kinetics, Vol. 35, Issue 7
  • DOI: 10.1002/kin.10127

Multiple benzene-formation paths in a fuel-rich cyclohexane flame
journal, November 2011

Benzene formation in premixed fuel-rich 1,3-butadiene flames
journal, January 2009

  • Hansen, Nils; Miller, James A.; Kasper, Tina
  • Proceedings of the Combustion Institute, Vol. 32, Issue 1
  • DOI: 10.1016/j.proci.2008.06.050

Pressure and Temperature Dependence of the Reaction of Vinyl Radical with Ethylene †
journal, July 2007

  • Ismail, Huzeifa; Goldsmith, C. Franklin; Abel, Paul R.
  • The Journal of Physical Chemistry A, Vol. 111, Issue 29
  • DOI: 10.1021/jp071041l

Kinetics of the reactions of CH2Br and CH2I radicals with molecular oxygen at atmospheric temperatures
journal, January 2006

  • Eskola, Arkke J.; Wojcik-Pastuszka, Dorota; Ratajczak, Emil
  • Physical Chemistry Chemical Physics, Vol. 8, Issue 12
  • DOI: 10.1039/b516291b

Kinetics of the Reaction of the CCl 2 Biradical with Molecular Chlorine
journal, November 2003

  • Kostina, Sofya A.; Shestov, Alexander A.; Knyazev, Vadim D.
  • The Journal of Physical Chemistry A, Vol. 107, Issue 48
  • DOI: 10.1021/jp0358432

Temperature-Dependent Kinetics of the Vinyl Radical (C 2 H 3 ) Self-Reaction
journal, February 2009

  • Ismail, Huzeifa; Abel, Paul R.; Green, William H.
  • The Journal of Physical Chemistry A, Vol. 113, Issue 7
  • DOI: 10.1021/jp8096132

Pressure and temperature dependence of the reaction of vinyl radical with alkenes II: Measured rates and predicted product distributions for vinyl+propene
journal, January 2009

  • Goldsmith, C. Franklin; Ismail, Huzeifa; Abel, Paul R.
  • Proceedings of the Combustion Institute, Vol. 32, Issue 1
  • DOI: 10.1016/j.proci.2008.06.142

Pressure and Temperature Dependence of the Reaction of Vinyl Radical with Alkenes III: Measured Rates and Predicted Product Distributions for Vinyl + Butene
journal, July 2009

  • Goldsmith, C. Franklin; Ismail, Huzeifa; Green, William H.
  • The Journal of Physical Chemistry A, Vol. 113, Issue 47
  • DOI: 10.1021/jp9042039

A simple and efficient CCSD(T)-F12 approximation
journal, December 2007

  • Adler, Thomas B.; Knizia, Gerald; Werner, Hans-Joachim
  • The Journal of Chemical Physics, Vol. 127, Issue 22
  • DOI: 10.1063/1.2817618

Simplified CCSD(T)-F12 methods: Theory and benchmarks
journal, February 2009

  • Knizia, Gerald; Adler, Thomas B.; Werner, Hans-Joachim
  • The Journal of Chemical Physics, Vol. 130, Issue 5
  • DOI: 10.1063/1.3054300

Exploring the Limit of Accuracy of the Global Hybrid Meta Density Functional for Main-Group Thermochemistry, Kinetics, and Noncovalent Interactions
journal, October 2008

  • Zhao, Yan; Truhlar, Donald G.
  • Journal of Chemical Theory and Computation, Vol. 4, Issue 11
  • DOI: 10.1021/ct800246v

Effectiveness of Diffuse Basis Functions for Calculating Relative Energies by Density Functional Theory
journal, March 2003

  • Lynch, Benjamin J.; Zhao, Yan; Truhlar, Donald G.
  • The Journal of Physical Chemistry A, Vol. 107, Issue 9
  • DOI: 10.1021/jp021590l

Advances in methods and algorithms in a modern quantum chemistry program package
journal, January 2006

  • Shao, Yihan; Molnar, Laszlo Fusti; Jung, Yousung
  • Phys. Chem. Chem. Phys., Vol. 8, Issue 27
  • DOI: 10.1039/B517914A

Computational Thermochemistry: Scale Factor Databases and Scale Factors for Vibrational Frequencies Obtained from Electronic Model Chemistries
journal, August 2010

  • Alecu, I. M.; Zheng, Jingjing; Zhao, Yan
  • Journal of Chemical Theory and Computation, Vol. 6, Issue 9
  • DOI: 10.1021/ct100326h

Development of density functionals for thermochemical kinetics
journal, August 2004

  • Boese, A. Daniel; Martin, Jan M. L.
  • The Journal of Chemical Physics, Vol. 121, Issue 8
  • DOI: 10.1063/1.1774975

Ab initio statistical thermodynamical models for the computation of third-law entropies
journal, April 1997

  • East, Allan L. L.; Radom, Leo
  • The Journal of Chemical Physics, Vol. 106, Issue 16
  • DOI: 10.1063/1.473958

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

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

Theoretical Unimolecular Kinetics for CH 4 + M ⇄ CH 3 + H + M in Eight Baths, M = He, Ne, Ar, Kr, H 2 , N 2 , CO, and CH 4
journal, June 2011

  • Jasper, Ahren W.; Miller, James A.
  • The Journal of Physical Chemistry A, Vol. 115, Issue 24
  • DOI: 10.1021/jp200048n

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

Photochemical and Discharge-Driven Pathways to Aromatic Products from 1,3-Butadiene
journal, November 2007

  • Newby, Josh J.; Stearns, Jaime A.; Liu, Ching-Ping
  • The Journal of Physical Chemistry A, Vol. 111, Issue 43
  • DOI: 10.1021/jp0752567

Formation of fulvene in the reaction of C2H with 1,3-butadiene
journal, February 2015

  • Lockyear, Jessica F.; Fournier, Martin; Sims, Ian R.
  • International Journal of Mass Spectrometry, Vol. 378
  • DOI: 10.1016/j.ijms.2014.08.025

Absorption Spectrum and Cross Sections of the Allyl Radical Measured Using Cavity Ring-Down Spectroscopy:  The à ← X̃ Band
journal, September 2000

  • Tonokura, Kenichi; Koshi, Mitsuo
  • The Journal of Physical Chemistry A, Vol. 104, Issue 37
  • DOI: 10.1021/jp001129y

Ultraviolet photodissociation of vinyl iodide: understanding the halogen dependence of photodissociation mechanisms in vinyl halides
journal, January 2008

  • Zou, Peng; Strecker, Kevin E.; Ramirez-Serrano, Jaime
  • Phys. Chem. Chem. Phys., Vol. 10, Issue 5
  • DOI: 10.1039/B712117B

Direct Determination of the Simplest Criegee Intermediate (CH 2 OO) Self Reaction Rate
journal, June 2014

  • Buras, Zachary J.; Elsamra, Rehab M. I.; Green, William H.
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 13
  • DOI: 10.1021/jz5008406

Vinyl radical visible spectroscopy and excited state dynamics
journal, January 2002

  • Shahu, Milena; Yang, Chun-Hui; Pibel, Charles D.
  • The Journal of Chemical Physics, Vol. 116, Issue 19
  • DOI: 10.1063/1.1471909

Direct Kinetic Measurements of Reactions between the Simplest Criegee Intermediate CH 2 OO and Alkenes
journal, March 2014

  • Buras, Zachary J.; Elsamra, Rehab M. I.; Jalan, Amrit
  • The Journal of Physical Chemistry A, Vol. 118, Issue 11
  • DOI: 10.1021/jp4118985

A theoretical and experimental kinetic study of phenyl radical addition to butadiene
journal, January 2005

Reaction of Phenyl Radicals with Acetylene:  Quantum Chemical Investigation of the Mechanism and Master Equation Analysis of the Kinetics
journal, September 2003

  • Tokmakov, I. V.; Lin, M. C.
  • Journal of the American Chemical Society, Vol. 125, Issue 37
  • DOI: 10.1021/ja0301121

Near-threshold absolute photoionization cross-sections of some reaction intermediates in combustion
journal, February 2008

  • Wang, Juan; Yang, Bin; Cool, Terrill A.
  • International Journal of Mass Spectrometry, Vol. 269, Issue 3
  • DOI: 10.1016/j.ijms.2007.10.013

Vacuum Ultraviolet Photoionization Mass Spectra and Cross-Sections for Volatile Organic Compounds at 10.5 eV
journal, August 2007

Collisional deactivation of vibrationally highly excited polyatomic molecules. II. Direct observations for excited toluene
journal, June 1983

  • Hippler, H.; Troe, J.; Wendelken, H. J.
  • The Journal of Chemical Physics, Vol. 78, Issue 11
  • DOI: 10.1063/1.444670
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Automated reaction database and reaction network analysis: extraction of reaction templates using cheminformatics
    journal, March 2018

    • Plehiers, Pieter P.; Marin, Guy B.; Stevens, Christian V.
    • Journal of Cheminformatics, Vol. 10, Issue 1
    • DOI: 10.1186/s13321-018-0269-8
      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: