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Title: Isomerization and Fragmentation of Cyclohexanone in a Heated Micro-Reactor

Abstract

Here, the thermal decomposition of cyclohexanone (C6H10=O) has been studied in a set of flash-pyrolysis microreactors. Decomposition of the ketone was observed when dilute samples of C6H10=O were heated to 1200 K in a continuous flow microreactor. Pyrolysis products were detected and identified by tunable VUV photoionization mass spectroscopy and by photoionization appearance thresholds. Complementary product identification was provided by matrix infrared absorption spectroscopy. Pyrolysis pressures were roughly 100 Torr, and contact times with the microreactors were roughly 100 μs. Thermal cracking of cyclohexanone appeared to result from a variety of competing pathways, all of which open roughly simultaneously. Isomerization of cyclohexanone to the enol, cyclohexen-1-ol (C6H9OH), is followed by retro-Diels–Alder cleavage to CH2=CH2 and CH2=C(OH)–CH=CH2. Further isomerization of CH2=C(OH)–CH=CH2 to methyl vinyl ketone (CH3CO–CH=CH2, MVK) was also observed. Photoionization spectra identified both enols, C6H9OH and CH2=C(OH)–CH=CH2, and the ionization threshold of C6H9OH was measured to be 8.2 ± 0.1 eV. Coupled cluster electronic structure calculations were used to establish the energetics of MVK. The heats of formation of MVK and its enol were calculated to be ΔfH298(cis-CH3CO–CH=CH2) = -26.1 ± 0.5 kcal mol–1 and ΔfH298(s-cis-1-CH2=C(OH)–CH=CH2) = -13.7 ± 0.5 kcal mol–1. The reaction enthalpy ΔrxnH298(C6H10=O → CH2=CH2 + s-cis-1-CH2=C(OH)–CH=CH2)more » is 53 ± 1 kcal mol–1 and ΔrxnH298(C6H10=O → CH2=CH2 + cis-CH3CO–CH=CH2) is 41 ± 1 kcal mol–1. At 1200 K, the products of cyclohexanone pyrolysis were found to be C6H9OH, CH2=C(OH)–CH=CH2, MVK, CH2CHCH2, CO, CH2=C=O, CH3, CH2=C=CH2, CH2=CH–CH=CH2, CH2=CHCH2CH3, CH2=CH2, and HC≡CH.« less

Authors:
 [1];  [2];  [1];  [1];  [3];  [3];  [3];  [2];  [4];  [1]
  1. Univ. of Colorado, Boulder, CO (United States). Dept. of Chemistry and Biochemistry
  2. Univ. of Texas, Austin, TX (United States). Dept. of Chemistry
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  4. Univ. of Colorado, Boulder, CO (United States). Center for Combustion and Environmental Research and Dept. of Mechanical Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Science Foundation (NSF); Robert A. Welch Foundation
OSTI Identifier:
1439183
Grant/Contract Number:  
AC02-05CH11231; CHE-1112466; CBET-1403979; F-1283; FG02-07ER15884
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: 51; Related Information: © 2015 American Chemical Society.; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 47 OTHER INSTRUMENTATION

Citation Formats

Porterfield, Jessica P., Nguyen, Thanh Lam, Baraban, Joshua H., Buckingham, Grant T., Troy, Tyler P., Kostko, Oleg, Ahmed, Musahid, Stanton, John F., Daily, John W., and Ellison, G. Barney. Isomerization and Fragmentation of Cyclohexanone in a Heated Micro-Reactor. United States: N. p., 2015. Web. doi:10.1021/acs.jpca.5b10984.
Porterfield, Jessica P., Nguyen, Thanh Lam, Baraban, Joshua H., Buckingham, Grant T., Troy, Tyler P., Kostko, Oleg, Ahmed, Musahid, Stanton, John F., Daily, John W., & Ellison, G. Barney. Isomerization and Fragmentation of Cyclohexanone in a Heated Micro-Reactor. United States. https://doi.org/10.1021/acs.jpca.5b10984
Porterfield, Jessica P., Nguyen, Thanh Lam, Baraban, Joshua H., Buckingham, Grant T., Troy, Tyler P., Kostko, Oleg, Ahmed, Musahid, Stanton, John F., Daily, John W., and Ellison, G. Barney. Mon . "Isomerization and Fragmentation of Cyclohexanone in a Heated Micro-Reactor". United States. https://doi.org/10.1021/acs.jpca.5b10984. https://www.osti.gov/servlets/purl/1439183.
@article{osti_1439183,
title = {Isomerization and Fragmentation of Cyclohexanone in a Heated Micro-Reactor},
author = {Porterfield, Jessica P. and Nguyen, Thanh Lam and Baraban, Joshua H. and Buckingham, Grant T. and Troy, Tyler P. and Kostko, Oleg and Ahmed, Musahid and Stanton, John F. and Daily, John W. and Ellison, G. Barney},
abstractNote = {Here, the thermal decomposition of cyclohexanone (C6H10=O) has been studied in a set of flash-pyrolysis microreactors. Decomposition of the ketone was observed when dilute samples of C6H10=O were heated to 1200 K in a continuous flow microreactor. Pyrolysis products were detected and identified by tunable VUV photoionization mass spectroscopy and by photoionization appearance thresholds. Complementary product identification was provided by matrix infrared absorption spectroscopy. Pyrolysis pressures were roughly 100 Torr, and contact times with the microreactors were roughly 100 μs. Thermal cracking of cyclohexanone appeared to result from a variety of competing pathways, all of which open roughly simultaneously. Isomerization of cyclohexanone to the enol, cyclohexen-1-ol (C6H9OH), is followed by retro-Diels–Alder cleavage to CH2=CH2 and CH2=C(OH)–CH=CH2. Further isomerization of CH2=C(OH)–CH=CH2 to methyl vinyl ketone (CH3CO–CH=CH2, MVK) was also observed. Photoionization spectra identified both enols, C6H9OH and CH2=C(OH)–CH=CH2, and the ionization threshold of C6H9OH was measured to be 8.2 ± 0.1 eV. Coupled cluster electronic structure calculations were used to establish the energetics of MVK. The heats of formation of MVK and its enol were calculated to be ΔfH298(cis-CH3CO–CH=CH2) = -26.1 ± 0.5 kcal mol–1 and ΔfH298(s-cis-1-CH2=C(OH)–CH=CH2) = -13.7 ± 0.5 kcal mol–1. The reaction enthalpy ΔrxnH298(C6H10=O → CH2=CH2 + s-cis-1-CH2=C(OH)–CH=CH2) is 53 ± 1 kcal mol–1 and ΔrxnH298(C6H10=O → CH2=CH2 + cis-CH3CO–CH=CH2) is 41 ± 1 kcal mol–1. At 1200 K, the products of cyclohexanone pyrolysis were found to be C6H9OH, CH2=C(OH)–CH=CH2, MVK, CH2CHCH2, CO, CH2=C=O, CH3, CH2=C=CH2, CH2=CH–CH=CH2, CH2=CHCH2CH3, CH2=CH2, and HC≡CH.},
doi = {10.1021/acs.jpca.5b10984},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 51,
volume = 119,
place = {United States},
year = {2015},
month = {11}
}

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Works referenced in this record:

Cyclic Oxygenates: A New Class of Second-Generation Biofuels for Diesel Engines?
journal, April 2009

  • Boot, Michael; Frijters, Peter; Luijten, Carlo
  • Energy & Fuels, Vol. 23, Issue 4
  • DOI: 10.1021/ef8003637

Soot and chemiluminescence in diesel combustion of bio-derived, oxygenated and reference fuels
journal, January 2009

  • Klein-Douwel, R. J. H.; Donkerbroek, A. J.; van Vliet, A. P.
  • Proceedings of the Combustion Institute, Vol. 32, Issue 2
  • DOI: 10.1016/j.proci.2008.06.140

Flash thermolysis. IV. Thermal fragmentation of cyclohexanone
journal, October 1970

  • De Mayo, Paul.; Verdun, D. L.
  • Journal of the American Chemical Society, Vol. 92, Issue 20
  • DOI: 10.1021/ja00723a055

Kinetics of oxidation of cyclohexanone in a jet-stirred reactor: Experimental and modeling
journal, January 2015


Computational Kinetic Study for the Unimolecular Decomposition Pathways of Cyclohexanone
journal, November 2014

  • Zaras, Aristotelis M.; Dagaut, Philippe; Serinyel, Zeynep
  • The Journal of Physical Chemistry A, Vol. 119, Issue 28
  • DOI: 10.1021/jp506227w

Enolization Enthalpies for Aliphatic Carbonyl and Thiocarbonyl Compounds
journal, July 1998

  • Zhang, Xian-Man; Malick, David; Petersson, George A.
  • The Journal of Organic Chemistry, Vol. 63, Issue 16
  • DOI: 10.1021/jo972157o

Thermodynamic Properties (Enthalpy, Bond Energy, Entropy, and Heat Capacity) and Internal Rotor Potentials of Vinyl Alcohol, Methyl Vinyl Ether, and Their Corresponding Radicals
journal, June 2006

  • da Silva, Gabriel; Kim, Chol-Han; Bozzelli, Joseph W.
  • The Journal of Physical Chemistry A, Vol. 110, Issue 25
  • DOI: 10.1021/jp0602878

Analysis of Potential Energy Surface for Butanone Isomerization
journal, October 2013


Unimolecular dissociation of cyclohexene at extremely high temperatures: behavior of the energy-transfer collision efficiency
journal, May 1987

  • Kiefer, John H.; Shah, Jatin N.
  • The Journal of Physical Chemistry, Vol. 91, Issue 11
  • DOI: 10.1021/j100295a076

The products of the thermal decomposition of CH 3 CHO
journal, July 2011

  • Vasiliou, AnGayle; Piech, Krzysztof M.; Zhang, Xu
  • The Journal of Chemical Physics, Vol. 135, Issue 1
  • DOI: 10.1063/1.3604005

The properties of a micro-reactor for the study of the unimolecular decomposition of large molecules
journal, September 2014

  • Guan, Qi; Urness, Kimberly N.; Ormond, Thomas K.
  • International Reviews in Physical Chemistry, Vol. 33, Issue 4
  • DOI: 10.1080/0144235X.2014.967951

Polarized Matrix Infrared Spectra of Cyclopentadienone: Observations, Calculations, and Assignment for an Important Intermediate in Combustion and Biomass Pyrolysis
journal, January 2014

  • Ormond, Thomas K.; Scheer, Adam M.; Nimlos, Mark R.
  • The Journal of Physical Chemistry A, Vol. 118, Issue 4
  • DOI: 10.1021/jp411257k

Pyrolysis of Cyclopentadienone: Mechanistic Insights from a Direct Measurement of Product Branching Ratios
journal, February 2015

  • Ormond, Thomas K.; Scheer, Adam M.; Nimlos, Mark R.
  • The Journal of Physical Chemistry A, Vol. 119, Issue 28
  • DOI: 10.1021/jp511390f

Biomass pyrolysis: Thermal decomposition mechanisms of furfural and benzaldehyde
journal, September 2013

  • Vasiliou, AnGayle K.; Kim, Jong Hyun; Ormond, Thomas K.
  • The Journal of Chemical Physics, Vol. 139, Issue 10
  • DOI: 10.1063/1.4819788

Unimolecular thermal decomposition of phenol and d 5 -phenol: Direct observation of cyclopentadiene formation via cyclohexadienone
journal, January 2012

  • Scheer, Adam M.; Mukarakate, Calvin; Robichaud, David J.
  • The Journal of Chemical Physics, Vol. 136, Issue 4
  • DOI: 10.1063/1.3675902

Chirped-pulse millimeter-wave spectroscopy for dynamics and kinetics studies of pyrolysis reactions
journal, January 2014

  • Prozument, Kirill; Barratt Park, G.; Shaver, Rachel G.
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 30
  • DOI: 10.1039/C3CP55352C

Chirped-Pulse Fourier Transform Microwave Spectroscopy Coupled with a Flash Pyrolysis Microreactor: Structural Determination of the Reactive Intermediate Cyclopentadienone
journal, June 2014

  • Kidwell, Nathanael M.; Vaquero-Vara, Vanesa; Ormond, Thomas K.
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 13
  • DOI: 10.1021/jz5010895

Pyrolysis of furan in a microreactor
journal, September 2013

  • Urness, Kimberly N.; Guan, Qi; Golan, Amir
  • The Journal of Chemical Physics, Vol. 139, Issue 12
  • DOI: 10.1063/1.4821600

The thermal decomposition of the benzyl radical in a heated micro-reactor. I. Experimental findings
journal, January 2015

  • Buckingham, Grant T.; Ormond, Thomas K.; Porterfield, Jessica P.
  • The Journal of Chemical Physics, Vol. 142, Issue 4
  • DOI: 10.1063/1.4906156

HEAT: High accuracy extrapolated ab initio thermochemistry
journal, December 2004

  • Tajti, Attila; Szalay, Péter G.; Császár, Attila G.
  • The Journal of Chemical Physics, Vol. 121, Issue 23
  • DOI: 10.1063/1.1811608

High-accuracy extrapolated ab initio thermochemistry. II. Minor improvements to the protocol and a vital simplification
journal, August 2006

  • Bomble, Yannick J.; Vázquez, Juana; Kállay, Mihály
  • The Journal of Chemical Physics, Vol. 125, Issue 6
  • DOI: 10.1063/1.2206789

High-accuracy extrapolated ab initio thermochemistry. III. Additional improvements and overview
journal, March 2008

  • Harding, Michael E.; Vázquez, Juana; Ruscic, Branko
  • The Journal of Chemical Physics, Vol. 128, Issue 11
  • DOI: 10.1063/1.2835612

Relatively Selective Production of the Simplest Criegee Intermediate in a CH 4 /O 2 Electric Discharge: Kinetic Analysis of a Plausible Mechanism
journal, November 2014

  • Nguyen, Thanh Lam; McCarthy, Michael C.; Stanton, John F.
  • The Journal of Physical Chemistry A, Vol. 119, Issue 28
  • DOI: 10.1021/jp510554g

Sums and Densities of Fully Coupled Anharmonic Vibrational States: A Comparison of Three Practical Methods
journal, February 2010

  • Nguyen, Thanh Lam; Barker, John R.
  • The Journal of Physical Chemistry A, Vol. 114, Issue 10
  • DOI: 10.1021/jp100132s

The effect of alkyl substitution on ionisation potential
journal, January 1971

  • Cocksey, B. J.; Eland, J. H. D.; Danby, C. J.
  • Journal of the Chemical Society B: Physical Organic
  • DOI: 10.1039/j29710000790

Interactions intramoléculaires en série cyclohexanique
journal, December 1976


Metastable ions characteristics. XVIII. Enolic C3H6O+ ion formed from aliphatic ketones
journal, July 1971

  • McLafferty, F. W.; McAdoo, D. J.; Smith, James S.
  • Journal of the American Chemical Society, Vol. 93, Issue 15
  • DOI: 10.1021/ja00744a028

Shock Tube and Theory Investigation of Cyclohexane and 1-Hexene Decomposition
journal, December 2009

  • Kiefer, J. H.; Gupte, K. S.; Harding, L. B.
  • The Journal of Physical Chemistry A, Vol. 113, Issue 48
  • DOI: 10.1021/jp905891q

Scale of acidities in the gas phase from methanol to phenol
journal, September 1979

  • Bartmess, John E.; Scott, Judith A.; McIver, Robert T.
  • Journal of the American Chemical Society, Vol. 101, Issue 20
  • DOI: 10.1021/ja00514a030

Atomic and Molecular Electron Affinities:  Photoelectron Experiments and Theoretical Computations
journal, January 2002

  • Rienstra-Kiracofe, Jonathan C.; Tschumper, Gregory S.; Schaefer, Henry F.
  • Chemical Reviews, Vol. 102, Issue 1
  • DOI: 10.1021/cr990044u

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

Rotationally resolved threshold photoelectron spectrum of the methyl radical
journal, February 1993

  • Blush, Joel A.; Chen, Peter; Wiedmann, Ralph T.
  • The Journal of Chemical Physics, Vol. 98, Issue 4
  • DOI: 10.1063/1.464077

Rotationally resolved pulsed field ionization photoelectron study of CO+(X 2Σ+,v+=0–42) in the energy range of 13.98–21.92 eV
journal, November 1999

  • Evans, M.; Ng, C. Y.
  • The Journal of Chemical Physics, Vol. 111, Issue 19
  • DOI: 10.1063/1.480259

Ionization from a double bond: Rovibronic photoionization dynamics of ethylene, large amplitude torsional motion and vibronic coupling in the ground state of C2H4+
journal, January 2004

  • Willitsch, S.; Hollenstein, U.; Merkt, F.
  • The Journal of Chemical Physics, Vol. 120, Issue 4
  • DOI: 10.1063/1.1635815

High-resolution threshold photoelectron study of the propargyl radical by the vacuum ultraviolet laser velocity-map imaging method
journal, December 2011

  • Gao, Hong; Xu, Yuntao; Yang, Lei
  • The Journal of Chemical Physics, Vol. 135, Issue 22
  • DOI: 10.1063/1.3664864

Molecular beam photoelectron spectroscopy of allene
journal, July 1990


Rovibrationally selected and resolved pulsed field ionization-photoelectron study of propyne: Ionization energy and spin-orbit interaction in propyne cation
journal, March 2008

  • Xing, Xi; Bahng, Mi-Kyung; Reed, Beth
  • The Journal of Chemical Physics, Vol. 128, Issue 9
  • DOI: 10.1063/1.2836429

Vacuum ultraviolet laser pulsed field ionization-photoelectron study of allyl radical CH2CHCH2
journal, May 2007

  • Xing, Xi; Reed, Beth; Lau, Kai-Chung
  • The Journal of Chemical Physics, Vol. 126, Issue 17
  • DOI: 10.1063/1.2737443

High resolution photoelectron spectroscopy and femtosecond intramolecular dynamics of H 2 CCO + and D 2 CCO +
journal, August 1993

  • Niu, Baohua; Bai, Ying; Shirley, David A.
  • The Journal of Chemical Physics, Vol. 99, Issue 4
  • DOI: 10.1063/1.465215

Torsional analyses of trans-2-butene and propene cations: A comparative investigation of two prototypical ions with different degrees of symmetry
journal, July 2001

  • Burrill, A. B.; Johnson, P. M.
  • The Journal of Chemical Physics, Vol. 115, Issue 1
  • DOI: 10.1063/1.1376634

Observation and assignment of the first photoelectron band of the CH3CO (X2A) radical
journal, March 2008

  • Zamanpour, M. H. N.; Bahkshandeh, A.; Ghaffarzadeh, S.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 162, Issue 3
  • DOI: 10.1016/j.elspec.2007.10.002

Ionization energies of formic and acetic acid monomers
journal, February 1974

  • Knowles, D. J.; Nicholson, A. J. C.
  • The Journal of Chemical Physics, Vol. 60, Issue 3
  • DOI: 10.1063/1.1681132

Enols Are Common Intermediates in Hydrocarbon Oxidation
journal, June 2005


The n s Rydberg series of 1,3‐ trans ‐butadiene observed using multiphoton ionization
journal, December 1983

  • Mallard, W. Gary; Miller, J. Houston; Smyth, Kermit C.
  • The Journal of Chemical Physics, Vol. 79, Issue 12
  • DOI: 10.1063/1.445770

Valence Ionization Energies of Hydrocarbons
journal, November 1977

  • Bieri, Gerhard; Burger, Fritz; Heilbronner, Edgar
  • Helvetica Chimica Acta, Vol. 60, Issue 7
  • DOI: 10.1002/hlca.19770600714

Étude par spectrométrie photoélectronique d'aldéhydes et de cétones éthyléniques conjugués
journal, January 1978


2-Hydroxybutadiene: Preparation, ionization energy and heat of formation
journal, January 1984


Simple method for assigning vibrational frequencies to rapidly equilibrating rotational isomers
journal, May 1972

  • Krantz, A.; Goldfarb, T. D.; Lin, C. Y.
  • Journal of the American Chemical Society, Vol. 94, Issue 11
  • DOI: 10.1021/ja00766a068

Polarized Infrared Absorption Spectra of Matrix-Isolated Allyl Radicals
journal, August 2001

  • Nandi, Sreela; Arnold, Pamela A.; Carpenter, Barry K.
  • The Journal of Physical Chemistry A, Vol. 105, Issue 32
  • DOI: 10.1021/jp011163s

Infrared Spectrum and Vibrational Potential Function of Ketene and the Deuterated Ketenes
journal, June 1963

  • Moore, C. Bradley; Pimentel, George C.
  • The Journal of Chemical Physics, Vol. 38, Issue 12
  • DOI: 10.1063/1.1733608

Works referencing / citing this record:

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journal, August 2017

  • Pastoors, Johan I. M.; Bodi, Andras; Hemberger, Patrick
  • Chemistry - A European Journal, Vol. 23, Issue 53
  • DOI: 10.1002/chem.201702376