High temperature pyrolysis of 2-methyl furan

Tranter, R. S.; Lynch, P. T.; Randazzo, J. B.; Lockhart, J. P. A.; Chen, X.; Goldsmith, C. F.

doi:10.1039/c7cp07775k

Title: High temperature pyrolysis of 2-methyl furan

Journal Article · Fri Feb 16 00:00:00 EST 2018 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/c7cp07775k· OSTI ID:1461436

^[1];

^[1]; Randazzo, J. B. ^[1]; Lockhart, J. P. A. ^[1]; Chen, X. ^[2];

^[1]

Argonne National Lab. (ANL), Argonne, IL (United States)
Brown Univ., Providence, RI (United States)

The dissociation of 2-methyl furan at high temperatures has been studied in a combined experimental and theoretical approach to elucidate the details of this multi-channel unimolecular reaction. Laser schlieren densitometry studies were performed in a diaphragmless shock tube over the range 1600 < T < 2300 K and three pressures 60, 120 and 240 Torr. The theoretical study identified many reaction paths, most of which are initiated by the formation of carbenes. Of these paths, five account for 99% consumption of 2MF, and three account for 95% consumption. Simulations of the experimental results with a model that incorporated the theoretical predictions of reaction paths failed to reproduce the experimental data. This was resolved by increasing the rate of loss of an H-atom from the methyl group in 2-methyl furan by a factor of 2–4. The resulting model provides good simulations of the complete set of experimental data. In conclusion, the branching fractions for the three key reactions are both temperature and pressure dependent.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1461436

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 20, Issue 16; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 14 works

Citation information provided by
Web of Science

References (54)

The pyrolysis of acetylene initiated by acetone Colket, M. B.; Seery, D. J.; Palmer, H. B. Combustion and Flame, Vol. 75, Issue 3-4 https://doi.org/10.1016/0010-2180(89)90048-5	journal	March 1989
Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography – Part II: 2-Methylfuran Tran, Luc-Sy; Togbé, Casimir; Liu, Dong Combustion and Flame, Vol. 161, Issue 3 https://doi.org/10.1016/j.combustflame.2013.05.027	journal	March 2014
Note: An improved driver section for a diaphragmless shock tube Randazzo, J. B.; Tranter, R. S. Review of Scientific Instruments, Vol. 86, Issue 1 https://doi.org/10.1063/1.4906758	journal	January 2015
An Experimental and Theoretical Study of the Thermal Decomposition of C ₄ H ₆ Isomers Lockhart, James P. A.; Goldsmith, C. Franklin; Randazzo, John B. The Journal of Physical Chemistry A, Vol. 121, Issue 20 https://doi.org/10.1021/acs.jpca.7b01186	journal	May 2017
Some Quantum‐Mechanical Considerations in the Theory of Reactions Involving an Activation Energy Hirschfelder, J. O.; Wigner, E. The Journal of Chemical Physics, Vol. 7, Issue 8 https://doi.org/10.1063/1.1750500	journal	August 1939
Very low pressure pyrolysis of furan, 2-methylfuran and 2,5-dimethylfuran. The stability of the furan ring Grela, M. A.; Amorebieta, V. T.; Colussi, A. J. The Journal of Physical Chemistry, Vol. 89, Issue 1 https://doi.org/10.1021/j100247a011	journal	January 1985
A simple and efficient CCSD(T)-F12 approximation Adler, Thomas B.; Knizia, Gerald; Werner, Hans-Joachim The Journal of Chemical Physics, Vol. 127, Issue 22 https://doi.org/10.1063/1.2817618	journal	December 2007
A complete basis set model chemistry. V. Extensions to six or more heavy atoms Ochterski, Joseph W.; Petersson, G. A.; Montgomery, J. A. The Journal of Chemical Physics, Vol. 104, Issue 7 https://doi.org/10.1063/1.470985	journal	February 1996
Multiple transition states in unimolecular reactions: A transition state switching model. Application to the C ₄ H ₈ ⁺ ⋅ system Chesnavich, Walter J.; Bass, Lewis; Su, Timothy The Journal of Chemical Physics, Vol. 74, Issue 4 https://doi.org/10.1063/1.441385	journal	February 1981
Combustion characteristics and emissions of 2-methylfuran compared to 2,5-dimethylfuran, gasoline and ethanol in a DISI engine Wang, Chongming; Xu, Hongming; Daniel, Ritchie Fuel, Vol. 103 https://doi.org/10.1016/j.fuel.2012.05.043	journal	January 2013
High-Temperature Study of 2-Methyl Furan and 2-Methyl Tetrahydrofuran Combustion: High-Temperature Combustion of 2-Methyl Furan and 2-Methyl Tetrahydrofuran Jouzdani, Shirin; Eldeeb, Mazen A.; Zhang, Lingshu International Journal of Chemical Kinetics, Vol. 48, Issue 9 https://doi.org/10.1002/kin.21008	journal	June 2016
Analysis of the Impact of 2-Methylfuran on Mixture Formation and Combustion in a Direct-Injection Spark-Ignition Engine Thewes, Matthias; Muether, Martin; Pischinger, Stefan Energy & Fuels, Vol. 25, Issue 12 https://doi.org/10.1021/ef201021a	journal	December 2011
Decomposition of 2-Methylfuran. Experimental and Modeling Study Lifshitz, Assa; Tamburu, Carmen; Shashua, Ronen The Journal of Physical Chemistry A, Vol. 101, Issue 6 https://doi.org/10.1021/jp962646c	journal	February 1997
Simple Chemical Transformation of Lignocellulosic Biomass into Furans for Fuels and Chemicals Binder, Joseph B.; Raines, Ronald T. Journal of the American Chemical Society, Vol. 131, Issue 5, p. 1979-1985 https://doi.org/10.1021/ja808537j	journal	February 2009
Experimental and Kinetic Modeling Study of 2-Methylfuran Pyrolysis at Low and Atmospheric Pressures Cheng, Zhanjun; He, Sirong; Xing, Lili Energy & Fuels, Vol. 31, Issue 1 https://doi.org/10.1021/acs.energyfuels.6b02399	journal	December 2016
The Dissociation of Diacetyl: A Shock Tube and Theoretical Study Yang, Xueliang; Jasper, Ahren W.; Kiefer, John H. The Journal of Physical Chemistry A, Vol. 113, Issue 29 https://doi.org/10.1021/jp903716f	journal	July 2009
A complete basis set model chemistry. VII. Use of the minimum population localization method Montgomery, J. A.; Frisch, M. J.; Ochterski, J. W. The Journal of Chemical Physics, Vol. 112, Issue 15 https://doi.org/10.1063/1.481224	journal	April 2000
Highly Selective Decarbonylation of 5-(Hydroxymethyl)furfural in the Presence of Compressed Carbon Dioxide Geilen, Frank M. A.; vom Stein, Thorsten; Engendahl, Barthel Angewandte Chemie International Edition, Vol. 50, Issue 30 https://doi.org/10.1002/anie.201007582	journal	June 2011
Single-step conversion of cellulose to 5-hydroxymethylfurfural (HMF), a versatile platform chemical Su, Yu; Brown, Heather M.; Huang, Xiwen Applied Catalysis A: General, Vol. 361, Issue 1-2, p. 117-122 https://doi.org/10.1016/j.apcata.2009.04.002	journal	June 2009
Ignition delay times of low alkylfurans at high pressures using a rapid compression machine Xu, Nan; Wu, Yingtao; Tang, Chenglong Proceedings of the Combustion Institute, Vol. 36, Issue 1 https://doi.org/10.1016/j.proci.2016.07.075	journal	January 2017
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals Zhao, Yan; Truhlar, Donald G. Theoretical Chemistry Accounts, Vol. 120, Issue 1-3 https://doi.org/10.1007/s00214-007-0310-x	journal	July 2007
Physical optics of the laser-schlieren shock tube technique Kiefer, J. H.; Al-Alami, M. Z.; Hajduk, J-C. Applied Optics, Vol. 20, Issue 2 https://doi.org/10.1364/AO.20.000221	journal	January 1981
Decomposition and Vibrational Relaxation in CH ₃ I and Self-Reaction of CH ₃ Radicals Yang, Xueliang; Goldsmith, C. Franklin; Tranter, Robert S. The Journal of Physical Chemistry A, Vol. 113, Issue 29 https://doi.org/10.1021/jp903336u	journal	July 2009
Combustion and Emissions of 2,5-Dimethylfuran in a Direct-Injection Spark-Ignition Engine Zhong, Shaohua; Daniel, Ritchie; Xu, Hongming Energy & Fuels, Vol. 24, Issue 5 https://doi.org/10.1021/ef901575a	journal	May 2010
Primary Combustion Intermediates in Lean and Rich Low-Pressure Premixed Laminar 2-Methylfuran/Oxygen/Argon Flames Wei, Lixia; Li, Zheming; Tong, Laihui Energy & Fuels, Vol. 26, Issue 11 https://doi.org/10.1021/ef301173z	journal	October 2012
Single Pulse Shock Tube Study of Allyl Radical Recombination Fridlyand, Aleksandr; Lynch, Patrick T.; Tranter, Robert S. The Journal of Physical Chemistry A, Vol. 117, Issue 23 https://doi.org/10.1021/jp402391n	journal	May 2013
The pyrolysis of 2-methylfuran: a quantum chemical, statistical rate theory and kinetic modelling study Somers, Kieran P.; Simmie, John M.; Metcalfe, Wayne K. Physical Chemistry Chemical Physics, Vol. 16, Issue 11 https://doi.org/10.1039/c3cp54915a	journal	January 2014
Predictions of pressure and temperature effects upon radical addition and recombination reactions Dean, A. M. The Journal of Physical Chemistry, Vol. 89, Issue 21 https://doi.org/10.1021/j100267a038	journal	October 1985
Unified statistical model for ’’complex’’ and ’’direct’’ reaction mechanisms Miller, William H. The Journal of Chemical Physics, Vol. 65, Issue 6 https://doi.org/10.1063/1.433379	journal	September 1976
Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates Román-Leshkov, Yuriy; Barrett, Christopher J.; Liu, Zhen Y. Nature, Vol. 447, Issue 7147, p. 982-985 https://doi.org/10.1038/nature05923	journal	June 2007
A comprehensive experimental and detailed chemical kinetic modelling study of 2,5-dimethylfuran pyrolysis and oxidation Somers, Kieran P.; Simmie, John M.; Gillespie, Fiona Combustion and Flame, Vol. 160, Issue 11 https://doi.org/10.1016/j.combustflame.2013.06.007	journal	November 2013
Shock-Tube Experiments and Kinetic Modeling of 2-Methylfuran Ignition at Elevated Pressure Wei, Liangjie; Tang, Chenglong; Man, Xingjia Energy & Fuels, Vol. 27, Issue 12 https://doi.org/10.1021/ef401809y	journal	November 2013
Direct, High-Yield Conversion of Cellulose into Biofuel Mascal, Mark; Nikitin, Edward B. Angewandte Chemie International Edition, Vol. 47, Issue 41 https://doi.org/10.1002/anie.200801594	journal	September 2008
Effect of spark timing and load on a DISI engine fuelled with 2,5-dimethylfuran Daniel, Ritchie; Tian, Guohong; Xu, Hongming Fuel, Vol. 90, Issue 2 https://doi.org/10.1016/j.fuel.2010.10.008	journal	February 2011
Reactivity Trends in Furan and Alkyl Furan Combustion Eldeeb, Mazen A.; Akih-Kumgeh, Benjamin Energy & Fuels, Vol. 28, Issue 10 https://doi.org/10.1021/ef501181z	journal	September 2014
Shock tube/time-of-flight mass spectrometer for high temperature kinetic studies Tranter, Robert S.; Giri, Binod R.; Kiefer, John H. Review of Scientific Instruments, Vol. 78, Issue 3 https://doi.org/10.1063/1.2437150	journal	March 2007
Quantitative detection of HCO behind shock waves: The thermal decomposition of HCO Friedrichs, Gernot; Herbon, John T.; Davidson, David F. Physical Chemistry Chemical Physics, Vol. 4, Issue 23 https://doi.org/10.1039/b205692e	journal	October 2002
Computational Study of the Combustion and Atmospheric Decomposition of 2-Methylfuran Davis, Alexander C.; Sarathy, S. Mani The Journal of Physical Chemistry A, Vol. 117, Issue 33 https://doi.org/10.1021/jp403085u	journal	July 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
Formation Enthalpies and Bond Dissociation Energies of Alkylfurans. The Strongest CX Bonds Known? Simmie, John M.; Curran, Henry J. The Journal of Physical Chemistry A, Vol. 113, Issue 17 https://doi.org/10.1021/jp810315n	journal	April 2009
Metal Chlorides in Ionic Liquid Solvents Convert Sugars to 5-Hydroxymethylfurfural Zhao, H.; Holladay, J. E.; Brown, H. Science, Vol. 316, Issue 5831, p. 1597-1600 https://doi.org/10.1126/science.1141199	journal	June 2007
Pyrolysis of Furan: Ab Initio Quantum Chemical and Kinetic Modeling Studies Sendt, Karina; Bacskay, George B.; Mackie, John C. The Journal of Physical Chemistry A, Vol. 104, Issue 9 https://doi.org/10.1021/jp993537b	journal	March 2000
5-Hydroxymethylfurfural (HMF) as a building block platform: Biological properties, synthesis and synthetic applications Rosatella, Andreia A.; Simeonov, Svilen P.; Frade, Raquel F. M. Green Chemistry, Vol. 13, Issue 4 https://doi.org/10.1039/c0gc00401d	journal	January 2011
Role of O ₂ + QOOH in Low-Temperature Ignition of Propane. 1. Temperature and Pressure Dependent Rate Coefficients Goldsmith, C. Franklin; Green, William H.; Klippenstein, Stephen J. The Journal of Physical Chemistry A, Vol. 116, Issue 13 https://doi.org/10.1021/jp210722w	journal	March 2012
Dissociation of C3H3I and rates for C3H3 combination at high temperatures Tranter, Robert S.; Yang, Xueliang; Kiefer, John H. Proceedings of the Combustion Institute, Vol. 33, Issue 1 https://doi.org/10.1016/j.proci.2010.05.030	journal	January 2011
Pyrolysis of methyl chloride, a pathway in the chlorine-catalyzed polymerization of methane Weissman, Maia; Benson, Sydney W. International Journal of Chemical Kinetics, Vol. 16, Issue 4 https://doi.org/10.1002/kin.550160403	journal	April 1984
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
Progress in detailed kinetic modeling of the combustion of oxygenated components of biofuels Tran, Luc Sy; Sirjean, Baptiste; Glaude, Pierre-Alexandre Energy, Vol. 43, Issue 1 https://doi.org/10.1016/j.energy.2011.11.013	journal	July 2012
Pyrolysis of Furan at Low Pressures: Vibrational Relaxation, Unimolecular Dissociation, and Incubation Times Fulle, D.; Dib, A.; Kiefer, J. H. The Journal of Physical Chemistry A, Vol. 102, Issue 38 https://doi.org/10.1021/jp9823042	journal	September 1998
Refractivity of combustion gases Gardiner, W. C.; Hidaka, Y.; Tanzawa, T. Combustion and Flame, Vol. 40 https://doi.org/10.1016/0010-2180(81)90124-3	journal	January 1981
Efficient and Accurate Double-Hybrid-Meta-GGA Density Functionals—Evaluation with the Extended GMTKN30 Database for General Main Group Thermochemistry, Kinetics, and Noncovalent Interactions Goerigk, Lars; Grimme, Stefan Journal of Chemical Theory and Computation, Vol. 7, Issue 2 https://doi.org/10.1021/ct100466k	journal	December 2010
A shock tube laser schlieren study of methyl acetate dissociation in the fall-off regime Annesley, Christopher J.; Franklin Goldsmith, C.; Tranter, Robert S. Physical Chemistry Chemical Physics, Vol. 16, Issue 16 https://doi.org/10.1039/c3cp55297g	journal	January 2014
Direct, High-Yield Conversion of Cellulose into Biofuel Mascal, Mark; Nikitin, Edward B. Angewandte Chemie, Vol. 120, Issue 41, p. 8042-8044 https://doi.org/10.1002/ange.200801594	journal	September 2008
Highly Selective Decarbonylation of 5-(Hydroxymethyl)furfural in the Presence of Compressed Carbon Dioxide Geilen, Frank M. A.; vom Stein, Thorsten; Engendahl, Barthel Angewandte Chemie, Vol. 123, Issue 30 https://doi.org/10.1002/ange.201007582	journal	June 2011

Cited By (1)

Mechanistic investigation of CO generation by pyrolysis of furan and its main derivatives Sun, Baizhong; Liang, Honglin; Che, Deyong RSC Advances, Vol. 9, Issue 16 https://doi.org/10.1039/c8ra10106j	journal	January 2019

Similar Records

Initiation reactions in the high temperature decomposition of styrene

Journal Article · Wed Sep 01 00:00:00 EDT 2021 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1461436

Sikes, Travis; Banyon, Colin; Schwind, Rachel A.; +4 more

An Experimental and Theoretical Study of the High Temperature Reactions of the Four Butyl Radical Isomers

Journal Article · Mon Sep 07 00:00:00 EDT 2020 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1461436

Randazzo, John B.; Sivaramakrishnan, Raghu; Jasper, Ahren W.; +3 more

A diaphragmless shock tube for high temperature kinetic studies

Journal Article · Mon Sep 15 00:00:00 EDT 2008 · Review of Scientific Instruments · OSTI ID:1461436

Tranter, Robert S; Giri, Binod R

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: High temperature pyrolysis of 2-methyl furan

Citation Formats

References (54)

Cited By (1)

Similar Records

Related Subjects