1. 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

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

3. 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, 1985-1991. not in literature

4. El-Nahas, A. M.; Simmie, J. M.; Navarro, M. V.; Bozzelli, J. W.; Black, G.; Curran, H. J. Phys. Chem. Chem. Phys. 2008, 10, 7139-7149. h or OH acetonyl O2O2 + OH dominant products (250-2000 K). 3-oxetanone in combustion/atmosphere

5. 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?

6. 3-oxetanone (0.015-0.4%) in argon <15 K CsI window for FTIR analysis 1 mm x 3.8 cm SiC tube @ 300–1700 K Supersonic jet of pyrolysis products and argon expanding into cryostat at 10 -6 Torr Pyrolysis and Matrix-Isolation FTIR

7. 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 tube @ 300–1700 K Pyrolysis and PIMS

8. Decomposition onsets below 600 º C. Temperature Study

9. + * Parent Peak ¤ Background Ketene Bands 3063 cm -1 2142 cm -1 976.6 cm -1 1200 ˚C pyrolysis * Parent Peak (3-oxetanone) ¤ Background 1200 ˚C pyrolysis Ketene

10. + Formaldehyde Bands 2802 cm -1 1742 cm -1 1499 cm -1 * Parent Peak (3-oxetanone) ¤ Background 1200 ˚C pyrolysis Formaldehyde

11. + C≡O * Parent Peak (3-oxetanone) ¤ Background Ethylene Oxide Bands 3077 cm -1 3020 cm -1 3010 cm -1 1273 cm -1 879 cm -1 877 cm -1 821 cm -1 816 cm -1 1200 ˚C pyrolysis Ethylene Oxide

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

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

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

15. Ethylene Peaks 2995 cm -1 1440 cm -1 947 cm -1 * Parent Peak (3-oxetanone) ¤ Background 1200 ˚C pyrolysis Ethylene

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

17. 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, 1782-1787. Joshi, A.; You, X.; Barckholtz, T. A.; Wang, H. J. Phys. Chem. A 2005, 109, 8016-8027. Setser, D. W. J. Phys. Chem. 1966, 70, 826-840. Reactions of Ethylene Oxide

18. 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 400-600 ˚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: 10.1021/acs.jpca.5b04565 Conclusions

19. Brian Warner B.S. 2015 Hannah Foreman B.S. 2014 Emily Wright B.S. 2015 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