REACTIONS OF 3-OXETANONE AT HIGH TEMPERATURES EMILY WRIGHT 1, BRIAN WARNER 1, HANNAH FOREMAN 1, KIMBERLY N. URNESS 2, LAURA R. McCUNN 1 1 Department of.

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REACTIONS OF 3-OXETANONE AT HIGH TEMPERATURES EMILY WRIGHT 1, BRIAN WARNER 1, HANNAH FOREMAN 1, KIMBERLY N. URNESS 2, LAURA R. McCUNN 1 1 Department of Chemistry, Marshall University, Huntington, WV 2 Department of Mechanical Engineering, University of Colorado-Boulder, Boulder, CO

ring puckering symmetry ring strain 3-oxetanone 67 th ISMS at Ohio State, 2012

How does 3-oxetanone decompose? + + C≡OC≡O ethylene oxide RRKM analysis* *Breuer, G. M.; Lewis, R. S.; Lee, E. K. C. J. Phys. Chem. 1975, 79, not in literature

El-Nahas, A. M.; Simmie, J. M.; Navarro, M. V.; Bozzelli, J. W.; Black, G.; Curran, H. J. Phys. Chem. Chem. Phys. 2008, 10, h or OH acetonyl O2O2 + OH dominant products ( K). 3-oxetanone in combustion/atmosphere

identify products of gas-phase pyrolysis of 3-oxetanone matrix-isolation FTIR and photoionization mass spectrometry (PIMS) detection temperature dependence of pyrolysis reactions fate of 3-oxetanone in atmosphere/combustion How does 3-oxetanone decompose?

3-oxetanone ( %) in argon <15 K CsI window for FTIR analysis 1 mm x 3.8 cm SiC 300–1700 K Supersonic jet of pyrolysis products and argon expanding into cryostat at Torr Pyrolysis and Matrix-Isolation FTIR

118.2 nm (10.5 eV) VUV photoionization 0.03% 3-oxetanone in 1500 Torr argon PIMS experiments by Kim Urness at U. Colorado, Boulder reflectron TOF mass spectrometer 1 mm x 3.8 cm SiC 300–1700 K Pyrolysis and PIMS

Decomposition onsets below 600 º C. Temperature Study

+ * Parent Peak ¤ Background Ketene Bands 3063 cm cm cm ˚C pyrolysis * Parent Peak (3-oxetanone) ¤ Background 1200 ˚C pyrolysis Ketene

+ Formaldehyde Bands 2802 cm cm cm -1 * Parent Peak (3-oxetanone) ¤ Background 1200 ˚C pyrolysis Formaldehyde

+ C≡O * Parent Peak (3-oxetanone) ¤ Background Ethylene Oxide Bands 3077 cm cm cm cm cm cm cm cm ˚C pyrolysis Ethylene Oxide

¤¤ * + C≡O Carbon Monoxide Band 2139 cm -1 * Parent Peak (3-oxetanone) ¤ Background 1200 ˚C pyrolysis Carbon Monoxide

+ + C≡OC≡O ethylene oxide Two decomposition channels observed

+ + CH 3 is a pyrolysis product PIMS of 3-oxetanone

Ethylene Peaks 2995 cm cm cm -1 * Parent Peak (3-oxetanone) ¤ Background 1200 ˚C pyrolysis Ethylene

CH 3 + CH 2 CH 2 + PIMS of Ethylene Oxide

Identified by FTIR and/or PIMS No evidence in FTIR or PIMS  CH 3 CHOCH 3 + H + CO CH 2 CH 2 + OH+ H Lifshitz, A.; Ben-Hamou, H. J. Phys. Chem. 1983, 87, Joshi, A.; You, X.; Barckholtz, T. A.; Wang, H. J. Phys. Chem. A 2005, 109, Setser, D. W. J. Phys. Chem. 1966, 70, Reactions of Ethylene Oxide

The following products have been identified: ketene, formaldehyde, ethylene oxide, carbon monoxide, methyl radical, and ethylene. The onset of the thermal decomposition for 3-oxetanone is between ˚C. The thermal decomposition of 3-oxetanone is not likely relevant to the atmospheric processing of acetone, but should be considered in combustion environments. Just accepted by Journal of Physical Chemistry A DOI: /acs.jpca.5b04565 Conclusions

Brian Warner B.S Hannah Foreman B.S Emily Wright B.S Kim Urness Barney Ellison Camille and Henry Dreyfus Foundation ACS Petroleum Research Fund Roger Combs Summer Research Fellowship Marshall University SURE Program National Science Foundation Acknowledgments