Isomerization and Fragmentation of Cyclohexanone in a Heated Micro-Reactor

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

doi:10.1021/acs.jpca.5b10984

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

Journal Article · 30 November 2015 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI: https://doi.org/10.1021/acs.jpca.5b10984 · OSTI ID:1439183

Porterfield, Jessica P. ^[1]; Nguyen, Thanh Lam ^[2]; Baraban, Joshua H. ^[1]; Buckingham, Grant T. ^[1]; Troy, Tyler P. ^[3]; Kostko, Oleg ^[3]; Ahmed, Musahid ^[3]; Stanton, John F. ^[2]; Daily, John W. ^[4]; Ellison, G. Barney ^[1]

Univ. of Colorado, Boulder, CO (United States). Dept. of Chemistry and Biochemistry
Univ. of Texas, Austin, TX (United States). Dept. of Chemistry
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Univ. of Colorado, Boulder, CO (United States). Center for Combustion and Environmental Research and Dept. of Mechanical Engineering

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 Δ_fH₂₉₈(cis-CH₃CO–CH=CH₂) = -26.1 ± 0.5 kcal mol^–1 and Δ_fH₂₉₈(s-cis-1-CH₂=C(OH)–CH=CH₂) = -13.7 ± 0.5 kcal mol^–1. The reaction enthalpy Δ_rxnH₂₉₈(C₆H₁₀=O → CH₂=CH₂ + s-cis-1-CH₂=C(OH)–CH=CH₂) is 53 ± 1 kcal mol^–1 and Δ_rxnH₂₉₈(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.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF); Robert A. Welch Foundation

Grant/Contract Number:: AC02-05CH11231; FG02-07ER15884

OSTI ID:: 1439183

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 51 Vol. 119; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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